Liquid-crystalline medium and high-frequency components comprising same

ABSTRACT

The present invention relates to liquid-crystalline media comprisingone or more chiral compounds andone or more compounds selected from the group of compounds of formulae I, II and III,in which the parameters have the meaning indicated in claim 1, and to components comprising these media for high-frequency technology, in particular phase shifters and microwave array antennas.

FIELD OF THE INVENTION

The present invention relates to liquid-crystalline media and to high-frequency components comprising same, especially microwave components for high-frequency devices, such as devices for shifting the phase of microwaves, in particular for microwave phased-array antennas.

Prior Art and Problem to be Solved

Liquid-crystalline media have a been used for some time in electro-optical displays (liquid crystal displays: LCDs) in order to display information.

Recently, however, liquid-crystalline media have also been proposed for use in components for microwave technology, such as, for example, in DE 102004029429.1 A and in JP 2005-120208 (A).

As a typical microwave application, the concept of the inverted microstrip line as described by K. C. Gupta, R. Garg, I. Bahl and P. Bhartia: Microstrip Lines and Slotlines, 2^(nd) ed., Artech House, Boston, 1996, is employed, for example, in D. Dolfi, M. Labeyrie, P. Joffre and J. P. Huignard: Liquid Crystal Microwave Phase Shifter. Electronics Letters, Vol. 29, No. 10, pp. 926-928, May 1993, N. Martin, N. Tentillier, P. Laurent, B. Splingart, F. Huert, P H. Gelin, C. Legrand: Electrically Microwave Tunable Components Using Liquid Crystals. 32^(nd) European Microwave Conference, pp. 393-396, Milan 2002, or in Weil, C.: Passiv steuerbare Mikrowellenphasenschieber auf der Basis nichtlinearer Dielektrika [Passively Controllable Microwave Phase Shifters based on Nonlinear Dielectrics], Darmstädter Dissertationen D17, 2002, C. Weil, G. Lüssem, and R. Jakoby: Tunable Invert-Microstrip Phase Shifter Device Using Nematic Liquid Crystals, IEEE MTT-S Int. Microw. Symp., Seattle, Wash., June 2002, pp. 367-370, together with the commercial liquid crystal K15 from Merck KGaA. C. Weil, G. Lüssem, and R. Jakoby: Tunable Invert-Microstrip Phase Shifter Device Using Nematic Liquid Crystals, IEEE MTT-S Int. Microw. Symp., Seattle, Wash., June 2002, pp. 367-370, achieve phase shifter qualities of 12°/dB at 10 GHz with a control voltage of about 40 V therewith. The insertion losses of the LC, i.e. the losses caused only by the polarisation losses in the liquid crystal, are given as approximately 1 to 2 dB at 10 GHz in Weil, C.: Passiv steuerbare Mikrowellenphasenschieber auf der Basis nichtlinearer Dielektrika [Passively Controllable Microwave Phase Shifters based on Nonlinear Dielectrics], Darmstädter Dissertationen D17, 2002. In addition, it has been determined that the phase shifter losses are determined primarily by the dielectric LC losses and the losses at the waveguide junctions. T. Kuki, H. Fujikake, H. Kamoda and T. Nomoto: Microwave Variable Delay Line Using a Membrane Impregnated with Liquid Crystal. IEEE MTT-S Int. Microwave Symp. Dig. 2002, pp. 363-366, June 2002, and T. Kuki, H. Fujikake, T. Nomoto: Microwave Variable Delay Line Using Dual-Frequency Switching-Mode Liquid Crystal. IEEE Trans. Microwave Theory Tech., Vol. 50, No. 11, pp. 2604-2609, November 2002, also address the use of polymerised LC films and dual-frequency switching-mode liquid crystals in combination with planar phase shifter arrangements.

A. Penirschke, S. Müller, P. Scheele, C. Weil, M. Wittek, C. Hock and R. Jakoby: “Cavity Perturbation Method for Characterization of Liquid Crystals up to 35 GHz”, 34^(th) European Microwave Conference—Amsterdam, pp. 545-548 describe, inter alia, the properties of the known single liquid-crystalline substance K15 (Merck KGaA, Germany) at a frequency of 9 GHz.

A. Gaebler, F. Goelden, S. Müller, A. Penirschke and R. Jakoby “Direct Simulation of Material Permittivites using an Eigen-Susceptibility Formula-tion of the Vector Variational Approach”, 12MTC 2009—International Instrumentation and Measurement Technology Conference, Singapore, 2009 (IEEE), pp. 463-467, describe the corresponding properties of the known liquid-crystal mixture E7 (likewise Merck KGaA, Germany).

DE 102004029429.1 A describes the use of liquid-crystal media in microwave technology, inter alia in phase shifters. It has already investigated liquid-crystalline media with respect to their properties in the corresponding frequency range. In addition, it describes liquid-crystalline media which comprise a small amount of a single compound of the formula

respectively

in combination with the well known cyano biphenyl compound

and also media comprising, besides other compounds,

respectively

These relatively simple mixtures, however, show limited performance for the application in devices operating in the microwave regime and even need to be significantly be improved with respect to their general physical properties, such as, especially, the clearing point, the phase range, especially their stability against storage at low temperatures, and their viscosities, in particular their rotational viscosity.

Further liquid crystalline media for microwave applications comprising one or more these compounds, as well as similar ones, are proposed by for microwave applications in DE 102010025572 A and WO 2013/034227.

Polymer stabilization of liquid crystalline media, as well as doping by chiral dopants, has already been proposed for several types of display applications and for various reasons. However, there has been no respective suggestion for the type of applications envisaged by the instant application.

The known devices for the high frequency-technology comprising these media do still lack sufficient stability and, in particular, fast response.

However, these compositions are afflicted with serious disadvantages. Most of them result, besides other deficiencies, in disadvantageously high losses and/or inadequate phase shifts or inadequate material quality.

For these applications, liquid-crystalline media having particular, hitherto rather unusual and uncommon properties or combinations of properties are required.

Novel liquid-crystalline media having improved properties are thus necessary. In particular, the dielectric loss in the microwave region must be reduced and the material quality (η, sometimes also called figure of merit, short FoM), i.e. a high tunability and, at the same time, a low dielectric loss, must be improved. Besides these requirements increased focus has to be placed on improved response times for several envisaged applications especially for those devices using planar structures such as e.g. phase shifters and leaky antennas.

Polymer stabilization of liquid crystalline media, as well as doping by chiral dopants, has already been proposed for several types of display applications and for various reasons. However, there has been no respective suggestion for the type of applications envisaged by the instant application.

The known devices for the high frequency-technology comprising these media do still lack sufficient stability and, in particular, fast response.

However, these compositions are afflicted with serious disadvantages. Most of them result, besides other deficiencies, in disadvantageously high losses and/or inadequate phase shifts or inadequate material quality.

But for several applications also the response times have to be improved. This is obvious from the following. In the respective copmponents operating in the microwave regime, such as cavities and planar structures, such as micro strip antennas, typically use a liquid crystal material with a relatively large thickness. This thickness has a dimension of about 50 μm to about 250 μm, which would be an extremely large cell gap for an LCD. Typically the switching time of liquid crystals e.g. in electro-optical devices is proportional to the square of the cell gap (d²). This results in relatively long switching times of 1 to 2 minutes for a typical liquid crystal at ambient temperature.

In the field of liquid crystals it is well known to add a chiral dopant e.g. into a nematic liquid crystal host mixtures. At low concentrations of the chiral dopant a chiral-nematic phase, also called a cholesteric phase is obtained. Increased concentrations are used in order to achieve a higher degree of the chirality of the nematic phase required e.g. in super twist LCDs. At very high concentrations highly chiral media are obtained, which may even exhibit so called blue phases, which have a cubic orientational structure and are optically isotropic.

In electro-optical devices a general tendency of a decrease of the response time for switching off (τ_(off)) with increasing concentration of a chiral dopant is expected as disclosed e.g. in U.S. Pat. No. 4,141,947.

However, using chiral dopants in a nematic host in a higher concentration generally leads to optical effects in the optical spectrum, which may be desired or unwanted depending on the envisaged application. Most typical is the selective reflection of the cholesteric liquid crystals having a cholesteric pitch in the respective region. This effect is highly undesired in most applications of liquid crystals for electro-optical decices and in severe cases even limit their use in such applications.

While these effects in most cases negatively influence the operation of electro-optical devices they are not of that much concern for the performance of RF components operating in the microwave region based on liquid crystals.

Another aim of the invention is to extend the pool of suitable materials available to the expert. Other aims are immediately evident to the expert from the following description.

Surprisingly, it has now been found that by using a chiral additive also frequently called a chiral dopant, respectively of one, two or more chiral additives, the response times and especially the “switching off times” (abbrev. τ_(off)) of the media in the devices can be significantly reduced compared to the state of the art.

Preferably the chiral dopants present in the media according to the ionstant application are mesogenic compounds and most preferably they exhibit a mesophase on their own.

Particularly preferred the media according to the present invention comprise one or more chiral dopants. Preferably these chiral dopants have an absolute value of the helical twisting power (short:HTP) in the range of 1 μm⁻¹ or more to 150 μm⁻¹ or less, preferably in the range from 10 μm⁻¹ or more to 100 μm⁻¹ or less. In case the media comprise at least two, i.e. two or more, chiral dopants, these may have mutually opposite signs of thier HTP-values. This condition is preferred for some specific embodiments, as it allows to compensate the chirality of the respective compounds to some degree and, thus, may be used to compensate various temperature dependent properties of the resulting media in the devices. Generally, however, it is preferred that most, or, even more preferred, all of the chiral compounds present in the media according to the present invention have the same sign of their HTP-values.

It has to be noted here that, as a first approximation, the HTP of a mixture of chiral compounds, i.e. of conventional chiral dopants, as well as of chiral reactive mesogens, may be approximated by the addition of their individual HTP values weighted by their respective concentrations in the medium.

In this embodiment, the cholesteric pitch of the modulation medium in the cholesteric phase, also referred to as the chiral nematic phase, can be reproduced to a first approximation by equation (1). P=(HTP·c)⁻¹  (1)

-   -   in which P denotes the cholesteric pitch,         -   c denotes the concentration of the chiral component (A) and         -   HTP (helical twisting power) is a constant which             characterises the twisting power of the chiral substance and             depends on the chiral substance (component (A)) and on the             achiral component (B).

If the pitch is to be determined more accurately, equation (1) can be correspondingly modified. To this end, the development of the cholesteric pitch in the form of a polynomial (2) is usually used. P=(HTP·c)⁻¹+(α₁ ·c)⁻²+(α₂ ·c)⁻³+ . . .   (2)

-   -   in which the parameters are as defined above for equation (1)         and α₁ and α₂ denote constants which depend on the chiral         component (A) and on the achiral component (B).

The polynomial can be continued up to the degree, which enables the desired accuracy.

Typically the parameters of the polynomial (HTP (sometimes also called α₁, α₂, α₃ and so forth) do depend more strongly on the type of the chiral dopant, and, to some degree, also on the specific liquid crystal mixture used.

Obviously, they do also depend on the enantiomeric excess of the respective chiral dopant. They have their respective largest absolute values for the pure enantiomers and are zero for racemates. In this application the values given are those for the pure enantiomers, having an enantiomeric excess of 98% or more, unless explicitly stated otherwise.

If the chiral component (A) consists of two or more compounds, equation (1) is modified to give equation (3). P=[Σ_(i)(HTP(i)·c _(i))]⁻¹  (3) in which P denotes the cholesteric pitch,

-   -   c_(i) denotes the concentration of the i-th compound of the         chiral component (A) and     -   HTP(i) denotes the HTP of the i-th compound of the chiral         component (A) in the achiral component (B).

The temperature dependence of the HTP is usually represented in a polynomial development (4), which, however, for practical purposes often can be terminated already right after the linear element (β₁). HTP(T)=HTP(T ₀)+β₁·(T−T ₀)+β₂·(T−T ₀)²+ . . .   (4)

-   -   in which the parameters are as defined above for equation (1)         and         -   T denotes the temperature,         -   T₀ denotes the reference temperature,         -   HTP(T) denotes the HTP at temperature T,         -   HTP(T₀) denotes the HTP at temperature T₀ and         -   β₁ and β₂ denote constants which depend on the chiral             component (A) and on the achiral component (B).

In addition, there is a steady demand for an improvement in the low-temperature behaviour of the components. Both an improvement in the operating properties at low temperatures and also in the shelf life are necessary here.

There is therefore a considerable demand for liquid-crystalline media having suitable properties for corresponding practical applications.

The invention additionally has the aim of providing improved methods and materials, to achieve polymer stabilised mesogenic phases, in particular nematic phases, which do not have the above-mentioned disadvantages of methods and materials described in prior art. These mesogenic phases comprise a polymer and a low molecular weight mesogenic material. Consequently, they are also called “composite systems”, or short “systems”.

Another aim of the invention is to extend the pool of suitable materials available to the expert. Other aims are immediately evident to the expert from the following description.

Additionally, it has been found that by using an RM, a stabilised liquid liquid crystalline phase which has improved, faster switching times, good tunability and acceptable loss can be achieved.

Additionally to mesogenic monomers the use of non-mesogenic monomers, such as 2-ethylhexylacrylate, is also possible and in certain instances may be beneficial. It, however, also may be problematic due to the volatile nature of such compounds, leading to problems of loss due to evaporation and inhomogeneity of the mixed monomer/host system.

Also, the use of non-mesogenic compounds can severely lower the clearing point of the liquid liquid crystalline host, leading to a much smaller width of the polymer stabilised nematic phase, which is not desirable for most practical applications.

Using RMs having a cyclohexylene core instead of a core comprising one or more 1,4-phenylenes has an advantage for the stability against UV irradiation in general and in particular against the UV irradiation used in the polymerisation process. The resultant polymer stabilised phase (composite system) therefore has a high voltage holding ratio (VHR).

Also, it has been found that by using cyclohexylene RMs in combination with a liquid liquid crystalline host comprising fluorophenyl liquid liquid crystalline compounds, the RMs do effectively stabilise this host to give a high VHR, which is necessary for advanced state-of-the-art devices.

Present Invention

Surprisingly, it has now been found that it is possible to achieve liquid-crystalline media having a suitably fast switching times, a suitable, nematic phase range and loss which do not have the disadvantages of the prior-art materials, or at least only do so to a considerably reduced extent.

These improved liquid-crystalline media in accordance with the present invention comprise

-   -   one or more chiral compounds     -   one or more compounds selected from the group of compounds of         formulae I, II and Ill

in which

-   R¹ denotes H, unfluorinated alkyl or unfluorinated alkoxy having 1     to 17, preferably having 3 to 10, C atoms or unfluorinated alkenyl,     unfluorinated alkenyloxy or unfluorinated alkoxyalkyl having 2 to     15, preferably 3 to 10, C atoms, preferably alkyl or unfluorinated     alkenyl, -   n denotes 0 or 1, preferably 1, and

-   -   independently of one another, denote

-   -   alternatively denotes

-   -   preferably

preferably

-   -   independently of one another, denote

more preferably

denotes

denotes

denotes

in which

-   R² denotes H, unfluorinated alkyl or unfluorinated alkoxy having 1     to 17, preferably having 3 to 10, C atoms or unfluorinated alkenyl,     unfluorinated alkenyloxy or unfluorinated alkoxyalkyl having 2 to     15, preferably 3 to 10, C atoms, preferably alkyl or unfluorinated     alkenyl, -   Z²¹ denotes trans-CH═CH—, trans-CF═CF— or —C≡C—, preferably —C≡C— or     trans-CH═CH—, and

-   -   independently of one another, denote

preferably

-   -   independently of one another, denote

preferably denotes

preferably denotes

-   -   more preferably

in which

-   R³ denotes H, unfluorinated alkyl or unfluorinated alkoxy having 1     to 17, preferably having 3 to 10, C atoms or unfluorinated alkenyl,     unfluorinated alkenyloxy or unfluorinated alkoxyalkyl having 2 to     15, preferably 3 to 10, C atoms, preferably alkyl or unfluorinated     alkenyl, -   one of Z³¹ and Z³², preferably Z³²; denotes trans-CH═CH—,     trans-CF═CF— or —C≡C— and the other one, independently thereof,     denotes trans-CH═CH—, trans-CF═CF— or a single bond, preferably one     of them, preferably Z³²; denotes —C≡C— or trans-CH═CH— and the other     denotes a single bond, and

-   -   independently of one another, denote

alternatively independently denotes e

preferably

-   -   independently of one another, denote

more preferably

denotes e

denotes e

and

-   -   more preferably

denotes e

-   -   more preferably

and

-   -   optionally one or more compounds of formula P         P^(a)—(Sp^(a))_(s1)-(A¹-Z¹)_(n1)-A²-Q-A³-(Z⁴-A⁴)_(n2)-(Sp^(b))_(s2)-P^(b)  P         wherein the individual radicals have the following meanings:

-   P^(a), P^(b) each, independently of one another, are a polymerisable     group,

-   Sp^(a), Sp^(b) each, independently of one another, denote a spacer     group,

-   s1, s2 each, independently of one another, denote 0 or 1,

-   n1, n2 each, independently of one another, denote 0 or 1, preferably     0,

-   Q denotes a single bond, —CF₂O—, —OCF₂—, —CH₂O—, —OCH₂—, —(CO)O—,     —O(CO)—, —(CH₂)₄—, —CH₂CH₂—, —CF₂—CF₂—, —CF₂—CH₂—, —CH₂—CF₂—,     —CH═CH—, —CF═CF—, —CF═CH—, —(CH₂)₃O—, —O(CH₂)₃—, —CH═CF—, —C≡C—,     —O—, —CH₂—, —(CH₂)₃—, —CF₂—, preferably —CF₂O—,

-   Z¹, Z⁴ denote a single bond, —CF₂O—, —OCF₂—, —CH₂O—, —OCH₂—,     —(CO)O—, —O(CO)—, —(CH₂)₄—, —CH₂CH₂—, —CF₂—CF₂—, —CF₂—CH₂—,     —CH₂—CF₂—, —CH═CH—, —CF═CF—, —CF═CH—, —(CH₂)₃O—, —O(CH₂)₃—, —CH═CF—,     —C≡C—, —O—, —CH₂—, —(CH₂)₃—, —CF₂—, where Z¹ and Q or Z⁴ and Q do     not simultaneously denote a group selected from —CF₂O— and —OCF₂—,

-   A¹, A², A³, A⁴     -   each, independently of one another, denote a diradical group         selected from the following groups:     -   a) the group consisting of trans-1,4-cyclohexylene,         1,4-cyclohexenylene and 1,4′-bicyclohexylene, in which, in         addition, one or more non-adjacent CH₂ groups may be replaced by         —O— and/or —S— and in which, in addition, one or more H atoms         may be replaced by F,     -   b) the group consisting of 1,4-phenylene and 1,3-phenylene, in         which, in addition, one or two CH groups may be replaced by N         and in which, in addition, one or more H atoms may be replaced         by L,     -   c) the group consisting of tetrahydropyran-2,5-diyl,         1,3-dioxane-2,5-diyl, tetrahydrofuran-2,5-diyl,         cyclobutane-1,3-diyl, piperidine-1,4-diyl, thiophene-2,5-diyl         and selenophene-2,5-diyl, each of which may also be mono- or         polysubstituted by L,     -   d) the group consisting of saturated, partially unsaturated or         fully unsaturated, and optionally substituted, polycyclic         radicals having 5 to 20 cyclic C atoms, one or more of which         may, in addition, be replaced by heteroatoms, preferably         selected from the group consisting of         bicyclo[1.1.1]pentane-1,3-diyl, bicyclo[2.2.2]octane-1,4-diyl,         spiro[3.3]heptane-2,6-diyl,

-   -    where, in addition, one or more H atoms in these radicals may         be replaced by L, and/or one or more double bonds may be         replaced by single bonds, and/or one or more CH groups may be         replaced by N,     -   and A³, alternatively may be a single bond,

-   L on each occurrence, identically or differently, denotes F, Cl, CN,     SCN, SF₅ or straight-chain or branched, in each case optionally     fluorinated, alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl,     alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms,

-   R⁰³, R⁰⁴ each, independently of one another, denote H, F or     straight-chain or branched alkyl having 1 to 12 C atoms, in which,     in addition, one or more H atoms may be replaced by F,

-   M denotes —O—, —S—, —CH₂—, —CHY¹— or —CY¹Y²—, and

-   Y¹ and Y² each, independently of one another, have one of the     meanings indicated above for R⁰, or denote Cl or CN, and one of the     groups Y¹ and Y² alternatively denotes —OCF₃, preferably H, F, Cl,     CN or CF₃,     as well as to a polymer stabilized system obtainable by     polymerisation of one or more compounds of formula P alone or in     combination with on or more further polymerisable compounds from a     respective mixture, and to the use of such a stabilized system in     components or devices for high frequency technology.

The chiral compounds of chiral component (A) preferably have a high absolute value of the HTP. They are also referred to as chiral dopants since they are generally added in relatively low concentrations to mesogenic base mixtures. They preferably have good solubility in the achiral component (B). They do not impair the mesogenic or liquid-crystalline properties of the mesogenic medium, or only do so to a small extent, so long as the cholesteric pitch has small values which are much smaller than the wavelength of the light. If the cholesteric pitch is in the order of the wavelength of the light and the temperature is within a defined range, however, they induce a blue phase having a completely different structure to that of the cholesteric phase. If two or more chiral compounds are employed, they may have the same or opposite direction of rotation and the same or opposite temperature dependence of the twist.

Particular preference is given to chiral compounds having an HTP of 20 μm⁻¹ or more, in particular of 40 μm⁻¹ or more, particularly preferably of 70 μm⁻¹ or more, in the commercial liquid-crystal mixture MLC-6828 from Merck KGaA.

In a preferred embodiment of the present invention, the chiral component (A) consists of two or more chiral compounds which all have the same sign of the HTP.

The temperature dependence of the HTP of the individual compounds may be high or low. The temperature dependence of the pitch of the medium can be compensated by mixing compounds having different temperature dependence of the HTP in corresponding ratios.

For the optically active component, a multiplicity of chiral dopants, some of which are commercially available, is available to the person skilled in the art, such as, for example, cholesteryl nonanoate, R/S-811, R/S-1011, R/S-2011, R/S-3011, R/S-4011, B(OC)2C*H—C-3 or CB15 (all Merck KGaA, Darmstadt).

Particularly suitable dopants are compounds which contain one or more chiral radicals and one or more mesogenic groups, or one or more aromatic or alicyclic groups which form a mesogenic group with the chiral radical.

Suitable chiral radicals are, for example, chiral branched hydrocarbon radicals, chiral ethanediols, binaphthols or dioxolanes, furthermore mono- or polyvalent chiral radicals selected from the group consisting of sugar derivatives, sugar alcohols, sugar acids, lactic acids, chiral substituted glycols, steroid derivatives, terpene derivatives, amino acids or sequences of a few, preferably 1-5, amino acids.

Preferred chiral radicals are sugar derivatives, such as glucose, mannose, galactose, fructose, arabinose and dextrose; sugar alcohols, such as, for example, sorbitol, mannitol, iditol, galactitol or anhydro derivatives thereof, in particular dianhydrohexitols, such as dianhydrosorbide (1,4:3,6-dianhydro-D-sorbide, isosorbide), dianhydromannitol (isosorbitol) or dianhydroiditol (isoiditol); sugar acids, such as, for example, gluconic acid, gulonic acid and ketogulonic acid; chiral substituted glycol radicals, such as, for example, mono- or oligoethylene or propylene glycols, in which one or more CH₂ groups are substituted by alkyl or alkoxy; amino acids, such as, for example, alanine, valine, phenylglycine or phenylalanine, or sequences of from 1 to 5 of these amino acids; steroid derivatives, such as, for example, cholesteryl or cholic acid radicals; terpene derivatives, such as, for example, menthyl, neomenthyl, campheyl, pineyl, terpineyl, isolongifolyl, fenchyl, carreyl, myrthenyl, nopyl, geraniyl, linaloyl, neryl, citronellyl or dihydrocitronellyl.

Suitable chiral radicals and mesogenic chiral compounds are described, for example, in DE 3425503, DE 3534777, DE 3534778, DE 3534779 and DE 3534780, DE 4342280, EP 01038941 and DE 19541820.

Chiral compounds preferably used according to the present invention are selected from the group consisting of the formulae shown below.

Particular preference is given to dopants selected from the group consisting of compounds of the following formulae A-I to A-III:

in which

-   R^(a11) and R^(a12), independently of one another, are alkyl,     oxaalkyl or alkenyl having from 2 to 9, preferably up to 7, carbon     atoms, and R^(a11) is alternatively methyl or alkoxy having from 1     to 9 carbon atoms, preferably both are alkyl, preferably n-alkyl, -   R^(a21) and R^(a22), independently of one another, are alkyl or     alkoxy having from 1 to 9, preferably up to 7, carbon atoms,     oxaalkyl, alkenyl or alkenyloxy having from 2 to 9, preferably up to     7, carbon atoms, preferably both are alkyl, preferably n-alkyl, -   R^(a31) and R^(a32), independently of one another, are alkyl,     oxaalkyl or alkenyl having from 2 to 9, preferably up to 7, carbon     atoms, and R^(a11) is alternatively methyl or alkoxy having from 1     to 9 carbon atoms, preferably both are alkyl, preferably n-alkyl.

Particular preference is given to dopants selected from the group consisting of the compounds of the following formulae:

Further preferred dopants are derivatives of the isosorbide, isomannitol or isoiditol of the following formula A-IV:

in which the group

is

(dianhydrosorbitol),

(dianhydromannitol), or

(dianhydroiditol), preferably dianhydrosorbitol, and chiral ethanediols, such as, for example, diphenylethanediol (hydrobenzoin), in particular mesogenic hydrobenzoin derivatives of the following formula A-V:

including the (R,S), (S,R), (R,R) and (S,S) enantiomers, which are not shown, in which

-   -   are each, independently of one another, 1,4-phenylene, which may         also be mono-, di- or trisubstituted by L, or 1,4-cyclo         hexylene,

-   L is H, F, Cl, CN or optionally halogenated alkyl, alkoxy,     alkylcarbonyl, alkoxycarbonyl or alkoxycarbonyloxy having 1-7 carbon     atoms,

-   c is 0 or 1,

-   Z₀ is —COO—, —OCO—, —CH₂CH₂— or a single bond, and

-   R⁰ is alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl or     alkylcarbonyloxy having 1-12 carbon atoms.

The compounds of the formula A-IV are described in WO 98/00428. The compounds of the formula A-V are described in GB-A-2,328,207.

Very particularly preferred dopants are chiral binaphthyl derivatives, as described in WO 02/94805, chiral binaphthol acetal derivatives, as described in WO 02/34739, chiral TADDOL derivatives, as described in WO 02/06265, and chiral dopants having at least one fluorinated bridging group and a terminal or central chiral group, as described in WO 02/06196 and WO 02/06195.

Particular preference is given to chiral compounds of the formula A-VI

in which

-   X¹, X², Y¹ and Y² are each, independently of one another, F, Cl, Br,     I, CN, SCN, SF₅, straight-chain or branched alkyl having from 1 to     25 carbon atoms, which may be monosubstituted or polysubstituted by     F, Cl, Br, I or CN and in which, in addition, one or more     non-adjacent CH₂ groups may each, independently of one another, be     replaced by —O—, —S—, —NH—, NR⁰—, —CO—, —COO—, —OCO—, —OCOO—,     —S—CO—, —CO—S—, —CH═CH— or —C≡C— in such a way that O and/or S atoms     are not bonded directly to one another, a polymerisable group or     cycloalkyl or aryl having up to 20 carbon atoms, which may     optionally be monosubstituted or polysubstituted by halogen,     preferably F, or by a polymerisable group, -   x¹ and x² are each, independently of one another, 0, 1 or 2, -   y¹ and y² are each, independently of one another, 0, 1, 2, 3 or 4, -   B¹ and B² are each, independently of one another, an aromatic or     partially or fully saturated aliphatic six-membered ring in which     one or more CH groups may be replaced by N atoms and one or more     non-adjacent CH₂ groups may be replaced by O and/or S, -   W¹ and W² are each, independently of one another,     —Z¹-A¹-(Z²-A²)_(m)-R, and one of the two is alternatively R¹ or A³,     but both are not simultaneously H, or

-   U¹ and U² are each, independently of one another, CH₂, O, S, CO or     CS, -   V¹ and V² are each, independently of one another, (CH₂)_(n), in     which from one to four non-adjacent CH₂ groups may be replaced by O     and/or S, and one of V¹ and V² and, in the case where

both are a single bond,

-   Z¹ and Z² are each, independently of one another, —O—, —S—, —CO—,     —COO—, —OCO—, —O—COO—, —CO—NR⁰—, —NR⁰—CO—, —O—CH₂—, —CH₂—O—,     —S—CH₂—, —CH₂—S—, —CF₂—O—, —O—CF₂—, —CF₂—S—, —S—CF₂—, —CH₂—CH₂—,     —CF₂—CH₂—, —CH₂—CF₂—, —CF₂—CF₂—, —CH═N—, —N═CH—, —N═N—, —CH═CH—,     —CF═CH—, —CH═CF—, —CF═CF—, —C≡C—, a combination of two of these     groups, where no two O and/or S and/or N atoms are bonded directly     to one another, preferably —CH═CH—COO—, or —COO—CH═CH—, or a single     bond, -   A¹, A² and A³ are each, independently of one another, 1,4-phenylene,     in which one or two non-adjacent CH groups may be replaced by N,     1,4-cyclohexylene, in which one or two non-adjacent CH₂ groups may     be replaced by O and/or S, 1,3-dioxolane-4,5-diyl,     1,4-cyclohexenylene, 1,4-bicyclo[2.2.2]octylene,     piperidine-1,4-diyl, naphthalene-2,6-diyl,     decahydronaphthalene-2,6-diyl or     1,2,3,4-tetrahydronaphthalene-2,6-diyl, where each of these groups     may be monosubstituted or polysubstituted by L, and in addition A¹     is a single bond, -   L is a halogen atom, preferably F, CN, NO₂, alkyl, alkoxy,     alkylcarbonyl, alkoxycarbonyl or alkoxycarbonyloxy having 1-7 carbon     atoms, in which one or more H atoms may be replaced by F or Cl, -   m is in each case, independently, 0, 1, 2 or 3, and -   R and R¹ are each, independently of one another, H, F, Cl, Br, I,     CN, SCN, SF₅, straight-chain or branched alkyl having from 1 or 3 to     25 carbon atoms respectively, which may optionally be     monosubstituted or polysubstituted by F, Cl, Br, I or CN, and in     which one or more non-adjacent CH₂ groups may be replaced by —O—,     —S—, —NH—, —NR⁰—, —CO—, —COO—, —OCO—, —O—COO—, —S—CO—, —CO—S—,     —CH═CH— or —C≡C—, where no two O and/or S atoms are bonded directly     to one another, or a polymerisable group.

Particular preference is given to chiral binaphthyl derivatives of the formula A-VI-1

in particular those selected from the following formulae A-VI-1a to A-VI-1c:

in which ring B and Z° are as defined for the formula A-IV, and

-   R⁰ as defined for formula A-iV or H or alkyl having from 1 to 4     carbon atoms, and -   b is 0, 1 or 2, -   and Z⁰ is, in particular, —OCO— or a single bond.

Particular p reference is furthermore given to chiral binaphthyl derivatives of the formula A-VI-2

in particular those selected from the following formulae A-VI-2a to A-VI-2f:

in which R⁰ is as defined for the formula A-VI, and X is H, F, Cl, CN or R⁰, preferably F.

Polymerisable compounds of formula P preferably used according to the present invention are selected from the group consisting of the following formulae:

in which L in each occurrence, identically or differently, has one of the meanings indicated above and below, r denotes 0, 1, 2, 3 or 4, s denotes 0, 1, 2 or 3, and n denotes an integer between 1 and 24, preferably between 1 and 12, very particularly preferably between 2 and 8, and in which, if a radical is not indicated at the end of a single or double bond, it is a terminal CH₃ or CH₂ group.

In the formulae P1 to P24,

preferably denotes a group selected from the group consisting of the following formulae:

particularly preferably selected from

The group A²-Q-A³ preferably denotes a group of the formula

in which at least one of the rings is substituted by at least one group L=F. r here is in each case, independently, preferably 0, 1 or 2.

P^(a) and P^(b) in the compounds of formula P and the sub-formulae thereof preferably denote acrylate or methacrylate, furthermore fluoroacrylate.

Sp^(a) and Sp^(b) in the compounds of formula P and the sub-formulae thereof preferably denote a radical selected from the group consisting of —(CH₂)_(p1)—, —(CH₂)_(p1)—O—, —(CH₂)_(p1)—O—CO— and —(CH₂)_(p1)—O—CO—O— and mirror images thereof, in which p1 denotes an integer from 1 to 12, preferably from 1 to 6, particularly preferably 1, 2 or 3, where these groups are linked to P^(a) or P^(b) in such a way that 0 atoms are not directly adjacent.

Of the compounds of formula P, particular preference is given to those in which

-   -   the radicals P^(a) and P^(b) are selected from the group         consisting of vinyloxy, acrylate, methacrylate, fluoroacrylate,         chloroacrylate, oxetane and epoxide groups, particularly         preferably acrylate or methacrylate groups,     -   the radicals Sp^(a) and Sp^(b) are selected from the group         consisting of —(CH₂)_(p1)—, —(CH₂)_(p1)—O—, —(CH₂)_(p1)—O—CO—         and —(CH₂)_(p1)—O—CO—O— and mirror images thereof, in which p1         denotes an integer from 1 to 12, preferably from 1 to 6,         particularly preferably 1, 2 or 3, and where these radicals are         linked to P^(a) or P^(b) in such a way that 0 atoms are not         directly adjacent, Compounds of formula P preferably used         according to a preferred embodiment of the instant invention are         those comprising exactly two rings (n1=n2=0), which are         preferably 6-membered rings. Especially preferred are compounds         selected from the group of compounds of the following formulae:

wherein P^(a), P^(b), Sp^(a), Sp^(b), s1 and s2 are as defined under formula P above, and preferably Sp^(a/b) is alkylene —(CH₂)_(n)— wherein n preferably is 3, 4, 5, 6 or 7 and P^(a/b) preferably a methacrylat- or acrylate moiety. Especially preferred is the use of compounds selected from the group of formulae Pa, Pb, Pc, Pd, Pe, Pf, Pg, Ph and Pi and, in particular the compounds of formula Pa.

In formula P the moiety “A²-Q-A³” preferably is a moiety of formula

wherein preferably at least one of the two phenylene rings is substituted by at least one L, which is different from H, wherein r is independently for each ring, and preferably it is for each ring 0, 1 or 2.

For the compounds of formula P, as well as for its respective sub-formulae, preferably

P^(a) and P^(b) are, independently from each other, acrylate or methacrylate, but also fluoroacrylate,

Sp^(a) and Sp^(b) are, independently from each other, —(CH₂)_(p1)—, —(CH₂)_(p1)—O—, —O—(CH₂)_(p1)—, —(CH₂)_(p1)—O—CO—, —CO—O—(CH₂)_(p1)—, —(CH₂)_(p1)—O—CO—O— or —(CH₂)_(p1)—O—CO—O—, wherein p1 is an integer from 1 to 12, preferably from 1 to 6, particularly preferred 1, 2 or 3, and wherein these moieties are linked with P^(a) or P^(b) in such a way that no O-atoms are linked directly to on another.

Especially preferred is the use of compounds of formula P, wherein

-   -   P^(a) and P^(b) are vinyleoxy-, acrylate-, methacrylata-,         fluoroacrylate-, chloroacrylate-, oxetane- or an epoxygroup,         particularly preferred acrylate- or methacrylate,     -   Sp^(a) and Sp^(b) are —(CH₂)_(p1)—, —(CH₂)_(p1)—O—,         —O—(CH₂)_(p1)—, —(CH₂)_(p1)—O—CO—, —CO—O—(CH₂)_(p1)—,         —(CH₂)_(p1)—O—CO—O— or —(CH₂)_(p1)—O—CO—O—, wherein p1 is an         integer from 1 to 12, preferably from 1 to 6, particularly         preferred 1, 2 or 3, and wherein these moieties are linked with         P^(a) or P^(b) in such a way that no O-atoms are linked directly         to on another.

Suitable and preferred co-monomers for use in polymer precursors for polymer stabilised devices according to the present invention are selected, for example, from the following formulae:

wherein the parameters have the following meanings:

-   P¹ and P² each, independently of one another, a polymerisable group,     preferably having one of the meanings given above or below for     P^(a), particularly preferred an acrylate, methacrylate,     fluoroacrylate, oxetane, vinyloxy- or epoxy group, -   Sp¹ and Sp² each, independently of one another, a single bond or a     spacer group, preferably having one of the meanings given above or     below for Sp^(a), particularly preferred an —(CH₂)_(p1)—,     —(CH₂)_(p1)—O—, —(CH₂)_(p1)—CO—O— or —(CH₂)_(p1)—O—CO—O—, wherein p1     is an integer from 1 to 12, and wherein the groups mentioned last     are linked to the adjacent ring via the 0-atom, -   and, wherein alternatively also one or more of P¹-Sp¹- and P²—Sp²-     may be R^(aa), provided that at least one of P¹—Sp¹- and P²—Sp²-     present in the compound is not R^(aa), -   R^(aa) H, F, Cl, CN or linear or branched alkyl having 1 to 25     C-atoms, wherein one or more non-adjacent —CH₂— groups,     independently of each another, may be replaced by —C(R⁰)═C(R⁰⁰)—,     —C≡C—, —N(R⁰)—, —O—, —S—, —CO—, —CO—O—, —O—CO—, —O—CO—O— in such a     way that neither O- nor S-atoms are directly linked to one another,     and wherein also one or more H-atoms may be replaced by F, Cl, CN or     P¹-Sp¹-, particularly preferred linear or branched, optionally     single- or polyfluorinated, alkyl, alkoxy, alkenyl, alkinyl,     alkylcarbonyl, alkoxycarbonyl, or alkylcarbonyloxy having 1 to 12     C-atoms, wherein the alkenyl- and alkinyl groups have at least two     and the branched groups have at least three C-atoms, -   R⁰, R⁰⁰ each, at each occurrence independently of one another, H or     alkyl having 1 to 12 C-atoms, -   R^(y) and R^(z) each, independently of one another, H, F, CH₃ or     CF₃, -   Z¹ —O—, —CO—, —C(R^(y)R^(z))—, or —CF₂CF₂—, -   Z² and Z³ each, independently of one another, —CO—O—, —O—CO—,     —CH₂O—, —OCH₂—, —CF₂O—, —OCF₂—, or —(CH₂)_(n)—, wherein n is 2, 3 or     4, -   L at each occurrence independently of one another, F, Cl, CN, SCN,     SF₅ or linear or branched, optionally mono- or polyfluorinated,     alkyl, alkoxy, alkenyl, alkinyl, alkylcarbonyl, alkoxycarbonyl,     alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C-atoms,     preferably F, -   L′ and L″ each, independently of one another, H, F or Cl, -   r 0, 1, 2, 3 or 4, -   s 0, 1, 2 or 3, -   t 0, 1 or 2, and -   λ 0 or 1.

Suitable and preferred co-monomers for use in devices according to the present application operable and/or operating at a temperature where the mesogenic medium is in the blue are for example selected from the group of mono-reactive compounds, which are present in the precursor of the polymer stabilised systems in a concentration in the range from 1 to 9 wt.-%, particularly preferred from 4 to 7 wt.-%. Preferred mono-reactive compounds are the compounds of formulae M1 bis M29, wherein one or more of P¹-Sp¹- and P²-Sp²- are Rest R^(aa), such that the compounds have a single reactive group only.

Particularly preferred mono-reactive compounds are the compounds of the following formulae

wherein P¹, Sp′ and R^(aa) have the respective meanings given above and P¹ preferably is acrylate (CH₂═CH—CO—O—) or methacrylate (CH₂═C(CH₃)—CO—O—).

Amongst these the compounds of formula

wherein

-   n is an integer, preferably an even integer, in the range from 1 to     16, preferably from 2 to 8, -   m is an integer in the range from 1 to 15, preferably from 2 to 7,     are especially preferred.

Particular preference is given to an LC medium, an LC device, preferably for the high frequency technology, in particular for a phase shifter or a microwave antenna e.g. a leaky antenna, a process or the use as described above and below, in which the LC medium or the polymerisable or polymerised component present therein comprises one or more compounds of the following formula:

in which P^(a), P^(b), Sp^(a), Sp^(b), s1, s2 and L have the meanings indicated above and below, r denotes 0, 1, 2, 3 or 4, and Z² and Z³ each, independently of one another, denote —CF₂—O— or —O—CF₂—, preferably Z² is —CF₂—O— and Z³ is —O—CF₂— or vice versa or Z² is —CO—O— and Z³ is —O—CO— or vice versa, and, most preferably, Z² is —CF₂—O— and Z³ is —O—CF₂— or Z² is —CO—O— and Z³ is —O—CO—.

Preferably the liquid-crystalline media used according to the present invention comprise as a polymer precursor or part of a polymer percursor one, two or more reactive mesogens, referably one or more mono-reactive mesogens and, at the same time, one or more direactive mesogens. Optionally one or more of the reactive mesogens may be replaced by a non-mesogenic, respectively an isotropic, reactive compound, preferably selected from HDMA, HDDMA, EHA, EA, EMA and the like.

In a preferred embodiment of the instant application the liquid-crystalline media used according to the present invention comprise a polymer obtained or obtainable by polymerisation, preferably photopolymerisation of a polymer precursor comprising one, two or more reactive mesogens, referably one or more mono-reactive mesogens and, at the same time, one or more direactive mesogens. Optionally one or more of the reactive mesogens may be replaced by a non-mesogenic, respectively an isotropic, reactive compound, preferably selected from 2-ethylhexyl acrylate (EHA), 1,3,3-trimethylhexyl acrylate (TMHA), hexanolediacrylate (HDDA), hexanoledimethacrylate (HDDMA), and the like, but also from metylmethacrylate (MMA), ethylacrylate (EA), ethylmethacrylate (EMA) and 6-(4′-cyanobiphenyl-4-yloxy)hexyl acrylate (6CBA), a mesogenic monomer.

Preferably one or more, most preferably all, mono-reactive mesogens are methacrylates and, also p referably one or more, most preferably all, mono-reactive mesogens are selected from the group of the bisacrylates and the mixed acrylates-methacrylates, preferably they are bisacrylates.

Preferably the liquid-crystalline media according to the present invention comprise

-   -   one or more compounds of formula I and     -   one or more compounds of formula II         or     -   one or more compounds of formula I and     -   one or more compounds of formula III or     -   one or more compounds of formula II and     -   one or more compounds of formula III         or, most preferably,     -   one or more compounds of formula I and     -   one or more compounds of formula II and     -   one or more compounds of formula III.

In a preferred embodiment of the present invention, the liquid-crystalline media comprise one or more compounds of formula I and one or more compounds of formula III.

In a further preferred embodiment of the present invention, the liquid-crystalline media comprise one or more compounds of formula I and one or more compounds of formula II.

The liquid-crystalline media in accordance with the present invention likewise preferably comprise one or more compounds of formula II and one or more compounds of formula III.

Particular preference is given in accordance with the present invention to liquid-crystalline media which comprise one or more compounds of formula I, one or more compounds of formula II and one or more compounds of formula III.

Additionally the liquid-crystalline media used according to the present invention in a certain embodiment preferably comprise one or more compounds of formula IV,

in which

denotes

preferably

particularly preferably

-   L⁴ denotes alkyl having 1 to 6 C atoms, cycloalkyl having 3 to 6 C     atoms or cycloalkenyl having 4 to 6 C atoms, preferably CH₃, C₂H₅,     n-C₃H₇ (—(CH₂)₂CH₃), i-C₃H₇ (—CH(CH₃)₂), cyclopropyl, cyclobutyl,     cyclohexyl, cyclopent-1-enyl or cyclohex-1-enyl, and particularly     preferably CH₃, C₂H₅, cyclopropyl or cyclobutyl, -   x⁴ denotes H, alkyl having 1 to 3 C atoms or halogen, preferably H,     F or Cl, and particularly preferably H or F and very particularly     preferably F, -   R⁴¹ to R⁴⁴, independently of one another, denote unfluorinated alkyl     or unfluorinated alkoxy, each having 1 to 15 C atoms, unfluorinated     alkenyl, unfluorinated alkenyloxy or unfluorinated alkoxyalkyl, each     having 2 to 15 C atoms, or cycloalkyl, alkylcycloalkyl,     cycloalkenyl, alkylcycloalkenyl, alkylcycloalkylalkyl or     alkylcyclo-alkenylalkyl, each having up to 15 C atoms, and     alternatively one of R⁴³ and R⁴⁴ or both also denote H,     preferably -   R⁴¹ and R⁴², independently of one another, denote unfluorinated     alkyl or unfluorinated alkoxy, each having 1 to 7 C atoms, or     unfluorinated alkenyl, unfluorinated alkenyloxy or unfluorinated     alkoxyalkyl, each having 2 to 7 C atoms,     particularly preferably -   R⁴¹ denotes unfluorinated alkyl having 1 to 7 C atoms or     unfluorinated alkenyl, unfluorinated alkenyloxy or unfluorinated     alkoxyalkyl, each having 2 to 7 C atoms, and     particularly preferably -   R⁴² denotes unfluorinated alkyl or unfluorinated alkoxy, each having     1 to 7 C atoms, and     preferably -   R⁴³ and R⁴⁴ denote H, unfluorinated alkyl having 1 to 5 C atoms,     unfluorinated cycloalkyl or cycloalkenyl having 3 to 7 C atoms,     unfluorinated alkylcyclohexyl or unfluorinated cyclohexylalkyl, each     having 4 to 12 C atoms, or unfluorinated alkylcyclohexylalkyl having     5 to 15 C atoms, particularly preferably cyclopropyl, cyclobutyl or     cyclohexyl, and very particularly preferably at least one of R⁴³ and     R⁴⁴ denotes n-alkyl, particularly preferably methyl, ethyl or     n-propyl, and the other denotes H or n-alkyl, particularly     preferably H, methyl, ethyl or n-propyl.

Preferably the liquid crystal media contain one or more chiral dopants preferably having an absolute value of the helical twisting power (HTP) of 20 μm⁻¹ or more, preferably of 40 μm⁻¹ or more, more preferably in the range of 60 μm⁻¹ or more, most preferably in the range of 80 μm⁻¹ or more to 260 μm⁻¹ or less.

The liquid-crystalline media in accordance with the present application preferably comprise in total 5% to 70%, preferably 5% to 60% and particularly preferably 30% to 50%, of compounds of formula I.

The liquid-crystalline media in accordance with the present application preferably comprise in total 20% to 80%, preferably 30% to 70% and particularly preferably 35% to 65%, of compounds of formula II.

The liquid-crystalline media in accordance with the present application preferably comprise in total 5% to 45%, preferably 10% to 40% and particularly preferably 15% to 35%, of compounds of formula III.

In a preferred embodiment of the present invention, in which the liquid-crystalline media comprise in each case one or more compounds of formulae I, II and III, the concentration of the compounds of formula I is preferably 45% to 100%, preferably 50% to 100% and particularly preferably 55% to 100%,

The concentration of the compounds of formula II is preferably 1% to 20%, preferably 2% to 15% and particularly preferably 3% to 10%, and the concentration of the compounds of formula III is preferably 1% to 30%, preferably 5% to 25% and particularly preferably 5% to 20%.

In a further preferred embodiment of the present invention, in which the liquid-crystalline media comprise in each case one or more compounds of the formulae I, II and III, the concentration of the compounds of formula I is preferably 15% to 40%, preferably 20% to 35% and particularly preferably 25% to 30%, the concentration of the compounds of formula II is preferably 10% to 35%, preferably 15% to 30% and particularly preferably 20% to 25% and the concentration of the compounds of formula III is preferably 25% to 50%, preferably 30% to 45% and particularly preferably 35% to 40%.

In a preferred embodiment of the present invention, in which the liquid-crystalline media comprise in each case one or more compounds of the formulae I and II, but at most 5% and preferably no compounds of formula III, the concentration of the compounds of formula I is preferably 10% to 50%, preferably 20% to 40% and particularly preferably 25% to 35% the concentration of the compounds of formula II is preferably 40% to 70% preferably 50% to 65% and particularly preferably 55% to 60%, and the concentration of the compounds of formula III is preferably 1% to 4%, preferably 1% to 3% and particularly preferably 0%.

The liquid-crystalline media in accordance with the present application particularly preferably comprise in total 50% to 80%, preferably 55% to 75% and particularly preferably 57% to 70% of compounds of formula I-1 and/or in total 5% to 70% preferably 6% to 50% and particularly preferably 8% to 20% of compounds selected from the group of the compounds of the formulae I-2 and I-3, most preferably compounds both of formula I-2 and of formula I-3.

The liquid-crystalline media in accordance with the present application likewise preferably comprise in total 5% to 60% preferably 10% to 50% and particularly preferably 7% to 20% of compounds of formula II.

In the case of the use of a single homologous compound, these limits correspond to the concentration of this homologue, which is preferably 2% to 20% particularly preferably 1% to 15%. In the case of the use of two or more homologues, the concentration of the individual homologues is likewise preferably in each case 1% to 15%

The compounds of the formulae I to III in each case include dielectrically positive compounds having a dielectric anisotropy of greater than 3, dielectrically neutral compounds having a dielectric anisotropy of less than 3 and greater than −1.5 and dielectrically negative compounds having a dielectric anisotropy of −1.5 or less.

In a preferred embodiment of the present invention, the liquid-crystal medium comprises one or more compounds of formula I, preferably selected from the group of the compounds of the formulae I-1 and I-2, preferably of the formulae I-1 and/or I-2, preferably simultaneously one or more compounds of formula I-1 and one or more compounds of formula I-2, and optionally, preferably obligatorily, one or more compounds of formula I-3, more preferably these compounds of formula I predominantly consist, even more preferably essentially consist and very particularly preferably completely consist thereof:

in which

-   L1 is H or F, preferably H     and the other parameters have the respective meanings indicated     above for formula I and preferably -   R¹ denotes unfluorinated alkyl having 1 to 7 C atoms or     unfluorinated alkenyl having 2 to 7 C atoms.

The media preferably comprise one or more compounds of formula I-1, which are preferably selected from the group of the compounds of the formulae I-1a to I-1c, preferably of formula I-1c, more preferably these compounds of formula I-1 predominantly consist, even more preferably essentially consist and very particularly preferably completely consist thereof:

in which the parameters have the respective meanings indicated above for formula I-1 and in which preferably

-   R¹¹ denotes alkyl or alkenyl.

The media preferably comprise one or more compounds of formula I-2, which are preferably selected from the group of the compounds of the formulae I-2a to I-2d, preferably of formula I-2d, more preferably these compounds of formula I-2 predominantly consist, even more preferably essentially consist and very particularly preferably completely consist thereof:

in which the parameters have the respective meanings indicated above for formula I-2 and in which preferably

-   R¹ denotes alkyl or alkenyl.

The media preferably comprise one or more compounds of formula I-3, which are preferably selected from the group of the compounds of the formulae I-3a to I-3d, preferably of formula I-3c, more preferably these compounds of formula I-2 predominantly consist, even more preferably essentially consist and very particularly preferably completely consist thereof:

in which the parameters have the respective meanings indicated above for formula I-2 and in which preferably

-   R¹ denotes alkyl or alkenyl.

In an even more preferred embodiment of the present invention, the compounds of formula I are selected from the group of the compounds I-1a and I-1b, preferably selected from the group of the compounds I-1c and I-1d, more preferably the compounds of formula I predominantly consist, even more preferably essentially consist and very particularly preferably completely consist thereof:

The media preferably comprise one or more compounds of formula II, which are preferably selected from the group of the compounds of the formulae II-1 to II-3, preferably selected from the group of the compounds of the formulae II-1 and II-2, more preferably these compounds of formula II predominantly consist, even more preferably essentially consist and very particularly preferably completely consist thereof:

in which the parameters have the meanings given under formula II above and preferably

-   R² denotes H, unfluorinated alkyl or alkoxy having 1 to 7 C atoms or     unfluorinated alkenyl having 2 to 7 C atoms,     and one of

denotes

-   -   and the other, independently denotes

preferably

-   -   most preferably

and preferably

-   R² denotes C_(n)H_(2n+1) or CH₂═CH—(CH₂)_(z), and -   z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.

The media preferably comprise one or more compounds of formula II-1, which are preferably selected from the group of the compounds of the formulae II-1a to II-1e, preferably selected from the group of the compounds of the formulae II-1a and II-1b, more preferably of formula II-1b, more preferably these compounds of formula II-1 predominantly consist, even more preferably essentially consist and very particularly preferably completely consist thereof:

in which

-   R² has the meaning indicated above and preferably denotes     C_(n)H_(2n+1) or CH₂═CH—(CH₂)_(z), and -   n and m, independently of one another, denote an integer in the     range from 0 to 15, preferably in the range from 1 to 7 and     particularly preferably 1 to 5, and -   z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.

The media preferably comprise one or more compounds of formula II-2, which are preferably selected from the group of the compounds of the formulae II-2a to II-2e, preferably selected from the group of the compounds of the formulae II-2a and II-2b, more preferably simultaneously one or more compounds of formula II-2a and one or more compounds of formula II-2b, more preferably these compounds of formula II-2 predominantly consist, even more preferably essentially consist and very particularly preferably completely consist thereof:

in which

-   R² has the meaning indicated above and preferably denotes     C_(n)H_(2n+1) or CH₂═CH—(CH₂)_(z), -   n and m, independently of one another, denote an integer in the     range from 0 to 15, preferably in the range from 1 to 7 and     particularly preferably 1 to 5, and -   z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.

The media preferably comprise one or more compounds of formula II-3, which are preferably selected from the group of the compounds of the of formulae II-3a to II-3e, preferably selected from the group of the compounds of formulae II-3a and II-3b, more preferably simultaneously one or more compounds of formula II-3a and one or more compounds of formula II-3b, more preferably these compounds of formula II-3 predominantly consist, even more preferably essentially consist and very particularly preferably completely consist thereof:

in which

-   R² has the meaning indicated above and preferably denotes     C_(n)H_(2n+1) or CH₂═CH—(CH₂)_(z), -   n and m, independently of one another, denote an integer in the     range from 0 to 15, preferably in the range from 1 to 7 and     particularly preferably 1 to 5, and -   z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.

The media preferably comprise one or more compounds of formula III, which are preferably selected from the group of the compounds of the formulae III-1 to III-6, more preferably these compounds of the formulae selected from the group of the compounds of the formulae III-1, III-1, III-2 and III-4, more preferably of formula III-1 and, even more preferably these compounds of formula III predominantly consist, even more preferably essentially consist and very particularly preferably completely consist thereof:

in which

-   Z³¹ and Z³² independently of one another denote trans-CH═CH— or     trans-CF═CF—, preferably trans-CH═CH—, and in formula II-6     alternatively one of Z³¹ and Z³² may denote —C≡C— and the other     parameters have the meaning given above under formula III, and     preferably -   R³ denotes H, unfluorinated alkyl or alkoxy having 1 to 7 C atoms or     unfluorinated alkenyl having 2 to 7 C atoms,     and one of

preferably

denotes

preferably

-   -   and the others, independently of one another, denote

preferably

more preferably

and preferably

-   R³ denotes C_(n)H_(2n+1) or CH₂═CH—(CH₂)_(z), -   n and m, independently of one another, denote an integer in the     range from 0 to 15, preferably in the range from 1 to 7 and     particularly preferably 1 to 5, and -   z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.

The media preferably comprise one or more compounds of formula II-1, which are preferably selected from the group of the compounds of the formulae III-1a to III-1d, preferably selected from the group of the compounds of the formulae III-1a and III-1b, more preferably of formula III-1b, and, even more preferably, these compounds of formula III-1 predominantly consist, even more preferably essentially consist and very particularly preferably completely consist thereof:

in which

-   R³ has the meaning indicated above and preferably denotes     C_(n)H_(2n+1) or CH₂═CH—(CH₂)_(z), -   n and m, independently of one another, denote an integer in the     range from 0 to 15, preferably in the range from 1 to 7 and     particularly preferably 1 to 5, and -   z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.

The media preferably comprise one or more compounds of formula III-2, which are preferably compounds of formula III-2a:

in which

-   R³ has the meaning indicated above and preferably denotes     C_(n)H_(2n+1) or CH₂═CH—(CH₂)_(z), -   n and m, independently of one another, denote an integer in the     range from 0 to 15, preferably in the range from 1 to 7 and     particularly preferably 1 to 5, and -   z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.

The media preferably comprise one or more compounds of formula III-3 and/or one or more compounds of formula III-4.

The media preferably comprise one or more compounds of formula III-5, which are preferably compounds of formula III-5a:

-   R³ has the meaning indicated above for formula III-5 and preferably     denotes C_(n)H_(2n+1), in which -   n denotes an integer in the range from 0 to 7, preferably in the     range from 1 to 5, and -   X²² denotes —F, —Cl, —OCF₃, —CN or —NCS, particularly preferably     —NCS.

Further preferred compounds of formula III are the compounds of the following formulae:

in which

-   n denotes an integer in the range from 0 to 7, preferably in the     range from 1 to 5.

Suitable and preferred polymerisation methods are, for example, thermally induced polymerization or photo polymerisation, preferably photopolymerisation, in particular UV photopolymerisation. One or more initiators can optionally also be added here. Suitable conditions for the polymerisation and suitable types and amounts of initiators are known to the person skilled in the art and are described in the literature. Suitable for free-radical polymerisation are, for example, and preferably, the commercially available photoinitiators Irgacure®184, Irgacure®369, Irgacure®651, Irgacure®784 (preferably), Irgacure®819 (preferably), Irgacure®907 or Irgacure®1300 (all from BASF) or Darocure®1173 (from Ciba AG). If an initiator is employed, its proportion is preferably 0.001% to 5% by weight, particularly preferably 0.001% to 1% by weight.

The polymerisable compounds according to the invention are also suitable for polymerisation without an initiator, which is accompanied by considerable advantages, such as, for example, lower material costs and in particular less contamination of the LC medium by possible residual amounts of the initiator or degradation products thereof. The polymerisation can thus also be carried out without the addition of an initiator. In a preferred embodiment, the LC medium thus comprises no polymerisation initiator.

The polymerisable component or the LC medium may also comprise one or more stabilisers in order to prevent undesired spontaneous polymerisation of the RMs, for example during storage or transport. Suitable types and amounts of stabilisers are known to the person skilled in the art and are described in the literature. Particularly suitable are, for example, the commercially available stabilisers from the Irganox® series (from Ciba AG), such as, for example, Irganox® 1076. If stabilisers are employed, their proportion, based on the total amount of the mixture of LS including the RMs or the polymerisable component, is preferably in the range from 10 ppm to 10,000 ppm, particularly preferably in the range from 50 ppm to 2,000 ppm, most preferably 0.2% or about 0.2%.

The mixtures are characterised as described below before the polymerisation. The reactive components are then polymerised by irradiation once (180 s), and the resultant media are re-characterised.

The polymerisation of the media preferably is carried out by irradiation with a UV lamp (e.g. Dymax, Bluewave 200, 365 nm interference filter) having an effective power of about 3.0 mW/cm² for 180 seconds. The polymerisation is carried out directly in the test cell/antenna device. To minimize UV induced host degradation a suitable long pass filter is beneficially applied, for example Schott GG395 or GG410.

The polymerisation is carried out at room temperature.

The entire irradiation time which results in maximum stabilisation is typically 180 s at the irradiation power indicated. Further polymerisations can be carried out in accordance with an optimised irradiation/temperature programme.

The total concentration of the polymerisable compounds in the medium prior to polymerisation preferably is in the range form 1% to 20%, more preferably from 2% to 15% and, most preferably from 2% to 10%.

In a preferred embodiment of the present invention, the medium comprises one or more dielectrically positive compounds of formula I-1 having a dielectric anisotropy of greater than 3.

The medium preferably comprises one or more dielectrically neutral compounds of formula I-2 having a dielectric anisotropy in the range from more than −1.5 to 3.

In a preferred embodiment of the present invention, the medium comprises one or more compounds of formula II.

In a further preferred embodiment of the present invention, the medium comprises one or more compounds of formula III.

The liquid-crystalline media, preferably or better the nematic component of the liquid ctrystalline media used in accordance with the present invention preferably comprise 10% or less, preferably 5% or less, particularly preferably 2% or less, very particularly preferably 1% or less, and in particular absolutely no compound having only two or fewer five- and/or six-membered rings.

The definitions of the abbreviations (acronyms) are likewise indicated below in Table D or are evident from Tables A to C.

The liquid-crystalline media in accordance with the present invention preferably comprise, more preferably predominantly consist of, even more preferably essentially consist of and very preferably completely consist of compounds selected from the group of the compounds of the formulae I to V, preferably I to IV and very preferably I to III and/or V.

In a preferred embodiment of the present inventin the liquid-crystalline media predominantly consist of, more preferably essentially consist of, and, most preferably completely consist of isothiocyanate compounds, preferably selected from the group of the compounds of the formulae I to III.

In this application, “comprise” in connection with compositions means that the entity in question, i.e. the medium or the component, comprises the component or components or compound or compounds indicated, preferably in a total concentration of 10% or more and very preferably 20% or more.

In this connection, “predominantly consist of” means that the entity in question comprises 55% or more, preferably 60% or more and very preferably 70% or more of the component or components or compound or compounds indicated.

In this connection, “essentially consist of” means that the entity in question comprises 80% or more, preferably 90% or more and very preferably 95% or more of the component or components or compound or compounds indicated.

In this connection, “completely consist of” means that the entity in question comprises 98% or more, preferably 99% or more and very preferably 100.0% of the component or components or compound or compounds indicated.

Other mesogenic compounds which are not explicitly mentioned above can optionally and advantageously also be used in the media in accordance with the present invention. Such compounds are known to the person skilled in the art.

Preferably the total concentration of the compounds of formulae I to III in the medium is in the range from 80% or more to 100%, more preferably in the range from 90% or more to 100% and most preferably in the range from 95% or more to 100%.

The total concentration of the compounds of formula I-3, preferably of the formula I-3c, in the media is in the range from 10% to 45% or less, more preferably from 15% or more to 35% or lessmore preferably from 20% or more to 33% or less and, most preferably from 25% or more to 30% or less.

The liquid-crystal media in accordance with the present invention preferably have a clearing point of 90° C. or more, more preferably 100° C. or more, still more preferably 120° C. or more, particularly preferably 150° C. or more and very particularly preferably 170° C. or more.

The nematic phase of the media in accordance with the invention preferably extends at least from 20° C. or less to 90° C. or more, preferably up to 100° C. or more, more preferably at least from 0° C. or less to 120° C. or more, very preferably at least from −10° C. or less to 140° C. or more and in particular at least from −20° C. or less to 150° C. or more.

The Δε of the liquid-crystal medium in accordance with the invention, at 1 kHz and 20° C., is preferably 1 or more, more preferably 2 or more and very preferably 3 or more.

The Δn of the liquid-crystal media in accordance with the present invention, at 589 nm (Na^(D)) and 20° C., is preferably in the range from 0.200 or more to 0.90 or less, more preferably in the range from 0.250 or more to 0.90 or less, even more preferably in the range from 0.300 or more to 0.85 or less and very particularly preferably in the range from 0.350 or more to 0.800 or less.

In a first preferred embodiment of the present application, the Δn of the liquid-crystal media in accordance with the present invention is preferably 0.50 or more, more preferably 0.55 or more.

In accordance with the present invention, the individual compounds of formula I are preferably used in a total concentration of 10% to 70%, more preferably 20% to 60%, even more preferably 30% to 50% and very preferably 25% to 45% of the mixture as a whole.

The compounds of formula II are preferably used in a total concentration of 1% to 20%, more preferably 1% to 15%, even more preferably 2% to 15% and very preferably 3% to 10% of the mixture as a whole.

The compounds of formula III are preferably used in a total concentration of 1% to 60%, more preferably 5% to 50%, even more preferably 10% to 45% and very preferably 15% to 40% of the mixture as a whole.

The liquid-crystal media preferably comprise, preferably predominantly consist of and very preferably completely consist of in total 50% to 100%, more preferably 70% to 100% and very preferably 80% to 100% and in particular 90% to 100% of the compounds of the formulae I, II, III, IV and V, preferably of the formulae I, III, IV and V, more preferably of the formulae I, II, III, IV and/or VI.

In the present application, the expression dielectrically positive describes compounds or components where Δε>3.0, dielectrically neutral describes those where −1.5≤Δε≤3.0 and dielectrically negative describes those where Δε<−1.5. Δε is determined at a frequency of 1 kHz and at 20° C. The dielectric anisotropy of the respective compound is determined from the results of a solution of 10% of the respective individual compound in a nematic host mixture. If the solubility of the respective compound in the host mixture is less than 10%, the concentration is reduced to 5%. The capacitances of the test mixtures are determined both in a cell having homeotropic alignment and in a cell having homogeneous alignment. The cell thickness of both types of cells is approximately 20 μm. The voltage applied is a rectangular wave having a frequency of 1 kHz and an effective value of typically 0.5 V to 1.0 V, but it is always selected to be below the capacitive threshold of the respective test mixture.

Δε is defined as (ε∥−ε_(⊥)), while ε_(ave.) is (ε∥+2ε_(⊥))/3.

The host mixture used for dielectrically positive compounds is mixture ZLI-4792 and that used for dielectrically neutral and dielectrically negative compounds is mixture ZLI-3086, both from Merck KGaA, Germany. The absolute values of the dielectric constants of the compounds are determined from the change in the respective values of the host mixture on addition of the compounds of interest. The values are extrapolated to a concentration of the compounds of interest of 100%.

Components having a nematic phase at the measurement temperature of 20° C. are measured as such, all others are treated like compounds.

The expression threshold voltage in the present application refers to the optical threshold and is quoted for 10% relative contrast (V₁₀), and the expression saturation voltage refers to the optical saturation and is quoted for 90% relative contrast (V₉₀), in both cases unless expressly stated otherwise. The capacitive threshold voltage (V₀), also called the Freeder-icks threshold (V_(Fr)), is only used if expressly mentioned.

The parameter ranges indicated in this application all include the limit values, unless expressly stated otherwise.

The different upper and lower limit values indicated for various ranges of properties in combination with one another give rise to additional preferred ranges.

Throughout this application, the following conditions and definitions apply, unless expressly stated otherwise. All concentrations are quoted in percent by weight and relate to the respective mixture as a whole, all temperatures are quoted in degrees Celsius and all temperature differences are quoted in differential degrees. All physical properties are determined in accordance with “Merck Liquid Crystals, Physical Properties of Liquid Crystals”, Status November 1997, Merck KGaA, Germany, and are quoted for a temperature of 20° C., unless expressly stated otherwise. The optical anisotropy (Δn) is determined at a wavelength of 589.3 nm. The dielectric anisotropy (Δε) is determined at a frequency of 1 kHz. The threshold voltages, as well as all other electro-optical properties, are determined using test cells produced at Merck KGaA, Germany. The test cells for the determination of Δε have a cell thickness of approximately 20 μm. The electrode is a circular ITO electrode having an area of 1.13 cm² and a guard ring. The orientation layers are SE-1211 from Nissan Chemicals, Japan, for homeotropic orientation (ε∥) and polyimide AL-1054 from Japan Synthetic Rubber, Japan, for homogeneous orientation (ε_(⊥)). The capacitances are determined using a Solatron 1260 frequency response analyser using a sine wave with a voltage of 0.3 V_(rms). The light used in the electro-optical measurements is white light. A set-up using a commercially available DMS instrument from Autronic-Melchers, Germany, is used here. The characteristic voltages have been determined under perpendicular observation. The threshold (V₁₀), mid-grey (V₅₀) and saturation (V₉₀) voltages have been determined for 10%, 50% and 90% relative contrast, respectively.

The liquid-crystalline media are investigated with respect to their properties in the microwave frequency range as described in A. Penirschke, S. Müller, P. Scheele, C. Weil, M. Wittek, C. Hock and R. Jakoby: “Cavity Perturbation Method for Characterization of Liquid Crystals up to 35 GHz”, 34^(th) European Microwave Conference—Amsterdam, pp. 545-548.

Compare in this respect also A. Gaebler, F. Gölden, S. Müller, A. Penirschke and R. Jakoby “Direct Simulation of Material Permittivites . . . ”, 12MTC 2009—International Instrumentation and Measurement Technology Conference, Singapore, 2009 (IEEE), pp. 463-467, and DE 102004029429 A, in which a measurement method is likewise described in detail.

The liquid crystal is introduced into a polytetrafluoroethylene (PTFE) capillary. The capillary has an internal radius of 180 μm and an external radius of 350 μm. The effective length is 2.0 cm. The filled capillary is introduced into the centre of the cavity with a resonance frequency of 30 GHz. This cavity has a length of 6.6 mm, a width of 7.1 mm and a height of 3.6 mm. The input signal (source) is then applied, and the result of the output signal is recorded using a commercial vector network analyser.

The change in the resonance frequency and the Q factor between the measurement with the capillary filled with the liquid crystal and the measurement without the capillary filled with the liquid crystal is used to deter-mine the dielectric constant and the loss angle at the corresponding target frequency by means of equations 10 and 11 in A. Penirschke, S. Müller, P. Scheele, C. Weil, M. Wittek, C. Hock and R. Jakoby: “Cavity Perturbation Method for Characterization of Liquid Crystals up to 35 GHz”, 34^(th) European Microwave Conference—Amsterdam, pp. 545-548, as described therein.

The values for the components of the properties perpendicular and parallel to the director of the liquid crystal are obtained by alignment of the liquid crystal in a magnetic field. To this end, the magnetic field of a permanent magnet is used. The strength of the magnetic field is 0.35 tesla. The alignment of the magnets is set correspondingly and then rotated correspondingly through 90°.

Preferred components are phase shifters, varactors, wireless and radio wave antenna arrays, matching circuit adaptive filters and others.

In the present application, the term compounds is taken to mean both one compound and a plurality of compounds, unless expressly stated otherwise.

The liquid-crystal media according to the invention preferably have nematic phases of in each case at least from −20° C. to 80° C., preferably from −30° C. to 85° C. and very particularly preferably from −40° C. to 100° C.

The phase particularly preferably extends to 120° C. or more, preferably to 140° C. or more and very particularly preferably to 180° C. or more. The expression have a nematic phase here means on the one hand that no smectic phase and no crystallisation are observed at low temperatures at the corresponding temperature and on the other hand that no clearing occurs on heating from the nematic phase. The investigation at low temperatures is carried out in a flow viscometer at the corresponding temperature and checked by storage in test cells having a layer thickness of 5 μm for at least 100 hours. At high temperatures, the clearing point is measured in capillaries by conventional methods.

Furthermore, the liquid-crystal media according to the invention are characterised by high optical anisotropy values in the visible range, especially at a wavelength of 589.0 nm (i.e. at the Na“D” line). The birefringence at 589 nm is preferably 0.20 or more, particularly preferably 0.25 or more, particularly preferably 0.30 or more, particularly preferably 0.40 or more and very particularly preferably 0.45 or more. In addition, the birefringence is preferably 0.80 or less.

The liquid crystals employed preferably have a positive dielectric anisotropy. This is preferably 2 or more, preferably 4 or more, particularly preferably 6 or more and very particularly preferably 10 or more.

Furthermore, the liquid-crystal media according to the invention are characterised by high anisotropy values in the microwave range. The birefringence at about 8.3 GHz is, for example, preferably 0.14 or more, particularly preferably 0.15 or more, particularly preferably 0.20 or more, particularly preferably 0.25 or more and very particularly preferably 0.30 or more. In addition, the birefringence is preferably 0.80 or less.

The dielectric anisotropy in the microwave range is defined as Δε_(r)≡(ε_(r,∥)−ε_(r,⊥)).

The tuneability (τ) is defined as τ≡(Δε_(r)/ε_(r,∥)).

The material quality (η) is defined as η≡(τ/tan δ_(εr,max)), where the maximum dielectric loss is tan δ_(εr,max.)≡max.{tan δ_(ε,r,⊥,);tan δ_(ε,r,∥)}.

The material quality (η) of the preferred liquid-crystal materials is 6 or more, preferably 8 or more, preferably 10 or more, preferably 15 or more, preferably 17 or more, preferably 20 or more, particularly preferably 25 or more and very particularly preferably 30 or more.

In the corresponding components, the preferred liquid-crystal materials have phase shifter qualities of 15°/dB or more, preferably 20°/dB or more, preferably 30°/dB or more, preferably 40°/dB or more, preferably 50°/dB or more, particularly preferably 80°/dB or more and very particularly preferably 100°/dB or more.

In some embodiments, however, liquid crystals having a negative value of the dielectric anisotropy can also advantageously be used.

The concentration of the chiral dopant, respectively the total concentration of the chiral dopants in the LC medium are preferably in the range from 0.001% or more to 20% or less, preferably from 0.05% or more to 5% or less, more preferably from 0.1% or more to 1% or less, and, most preferably from 0.2% or more to 0.8% or less. These preferred concnetratin ranges apply in particular to the chiral dopant S-2011, respectively to its enantiomeric form R-2011 (both from Merck KGaA) amnd for chiral dopants havein the same or a similar HTP. For Chiral dopants having either a higher or a lower absolute value of the HTP compared to S-2011 these preferred concentrations have to be decreased, respectively increased proportionally according to the ratio of their HTP values relatively to that of S-2011.

The liquid crystals employed are either individual substances or mixtures. They preferably have a nematic phase.

The concentration of the chiral dopant, respectively the total concentration of the chiral dopants in the LC medium are preferably in the range from 0.05% or more to 5% or less, more preferably from 0.1% or more to 1% or less, and, most preferably from 0.2% or more to 0.8% or less. These preferred concnetratin ranges apply in particular to the chiral dopant S-2011, respectively to its enantiomeric form R-2011 (both from Merck KGaA) amnd for chiral dopants havein the same or a similar HTP. For Chiral dopants having either a higher or a lower absolute value of the HTP compared to S-2011 these preferred concentrations have to be decreased, respectively increased proportionally according to the ratio of their HTP values relatively to that of S-2011.

The term “alkyl” preferably encompasses straight-chain and branched alkyl groups having 1 to 15 carbon atoms, in particular the straight-chain groups methyl, ethyl, propyl, butyl, pentyl, hexyl and heptyl. Groups having 2 to 10 carbon atoms are generally preferred.

The term “alkenyl” preferably encompasses straight-chain and branched alkenyl groups having 2 to 15 carbon atoms, in particular the straight-chain groups. Particularly preferred alkenyl groups are C₂- to C₇-1E-alkenyl, C₄- to C₇-3E-alkenyl, C₅- to C₇-4-alkenyl, C₆- to C₇-5-alkenyl and C₇-6-alkenyl, in particular C₂- to C₇-1E-alkenyl, C₄- to C₇-3E-alkenyl and C₅- to C₇-4-alkenyl. Examples of further preferred alkenyl groups are vinyl, 1E-propenyl, 1E-butenyl, 1E-pentenyl, 1E-hexenyl, 1E-heptenyl, 3-butenyl, 3E-pentenyl, 3E-hexenyl, 3E-heptenyl, 4-pentenyl, 4Z-hexenyl, 4E-hexenyl, 4Z-heptenyl, 5-hexenyl, 6-heptenyl and the like. Groups having up to 5 carbon atoms are generally preferred.

The term “fluoroalkyl” preferably encompasses straight-chain groups having a terminal fluorine, i.e. fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl and 7-fluoroheptyl. However, other positions of the fluorine are not excluded.

The term “oxaalkyl” or “alkoxyalkyl” preferably encompasses straight-chain radicals of the formula C_(n)H_(2n+1)—O—(CH₂)_(m), in which n and m each, independently of one another, denote 1 to 10. Preferably, n is 1 and m is 1 to 6.

Compounds containing a vinyl end group and compounds containing a methyl end group have low rotational viscosity.

In the present application, both high-frequency technology and hyper-frequency technology denote applications having frequencies in the range from 1 MHz to 1 THz, preferably from 1 GHz to 500 GHz, more preferably 2 GHz to 300 GHz, particularly preferably from about 5 GHz to 150 GHz.

The liquid-crystal media in accordance with the present invention may comprise further additives and chiral dopants in the usual concentrations. The total concentration of these further constituents is in the range from 0% to 10%, preferably 0.1% to 6%, based on the mixture as a whole. The concentrations of the individual compounds used are each preferably in the range from 0.1% to 3%. The concentration of these and similar additives is not taken into consideration when quoting the values and concentration ranges of the liquid-crystal components and liquid-crystal compounds of the liquid-crystal media in this application.

Preferably the media according to the present invention comprise one or more chiral compounds as chiral dopants in order to adjust their cholesteric pitch. Their total concentration in the media according to the instant invention is preferably in the range 0.1% to 15%, more preferably from 1% to 10% and most preferably from 2% to 6%.

The liquid-crystal media in accordance with the present invention may comprise further additives and chiral dopants in the usual concentrations. The total concentration of these further constituents is in the range from 0% to 10%, preferably 0.1% to 6%, based on the mixture as a whole. The concentrations of the individual compounds used are each preferably in the range from 0.1% to 3%. The concentration of these and similar additives is not taken into consideration when quoting the values and concentration ranges of the liquid-crystal components and liquid-crystal compounds of the liquid-crystal media in this application.

Preferably the media according to the present invention comprise one or more chiral compounds as chiral dopants in order to adjust their cholesteric pitch. Their total concentration in the media according to the instant invention is preferably in the range 0.1% to 15%, more preferably from 1% to 10% and most preferably from 2% to 6%.

Optionally the media according to the present invention may comprise further liquid crystal compounds in order to adjust the physical properties. Such compounds are known to the expert. Their concentration in the media according to the instant invention is preferably 0% to 30%, more preferably 0.1% to 20% and most preferably 1% to 15%.

The response times are given as rise time (τ_(on)) for the time for the change of the relative tuning, respectively of the relative contrast for the electo-optiocal response, from 0% to 90% (t₉₀−t₀), i.e. including the delay time (t₁₀−t₀), as decay time (T_(off)) for the time for the change of the relative tuning, respectively of the relative contrast for tre electo-optiocal response, from 100% back to 10% (t₁₀₀−t₁₀) and as the total response time (τ_(total))=τ_(on)+τ_(off)), respectively.

The liquid-crystal media according to the invention consist of a plurality of compounds, preferably 3 to 30, more preferably 4 to 20 and very preferably 4 to 16 compounds. These compounds are mixed in a conventional manner. In general, the desired amount of the compound used in the smaller amount is dissolved in the compound used in the larger amount. If the temperature is above the clearing point of the compound used in the higher concentration, it is particularly easy to observe completion of the dissolution process. It is, however, also possible to prepare the media in other conventional ways, for example using so-called pre-mixes, which can be, for example, homologous or eutectic mixtures of compounds, or using so-called “multibottle” systems, the constituents of which are themselves ready-to-use mixtures.

All temperatures, such as, for example, the melting point T(C,N) or T(C,S), the transition from the smectic (S) to the nematic (N) phase T(S,N) and the clearing point T(N,I) of the liquid crystals, are quoted in degrees Celsius. All temperature differences are quoted in differential degrees.

In the present invention and especially in the following examples, the structures of the mesogenic compounds are indicated by means of abbreviations, also referred to as acronyms. In these acronyms, the chemical formulae are abbreviated as follows using Tables A to C below. All groups C_(n)H_(2n+1), C_(m)H_(2m+1) and C_(l)H_(2l−1) or C_(n)H_(2n−1), C_(m)H_(2m−1) and C_(l)H_(2l−1) denote straight-chain alkyl or alkenyl, preferably 1-E-alkenyl, respectively, in each case having n, m or I C atoms. Table A lists the codes used for the ring elements of the core structures of the compounds, while Table B shows the linking groups. Table C gives the meanings of the codes for the left-hand or right-hand end groups. Table D shows illustrative structures of compounds with their respective abbreviations.

TABLE A Ring elements

C

D

DI

A

AI

P

G

GI

U

UI

Y

M

MI

N

NI

Np

N3f

N3fI

tH

tHI

tH2f

tH2fI

dH

K

KI

L

LI

F

FI

P(o)

PI(o)

P(i3)

PI(ic3)

P(t4)

PI(t4)

P(c3)

PI(c3)

P(c4)

PI(c4)

P(c5)

PI(c5)

P(e5)

PI(e5)

P(c6)

PI(c6)

P(e6)

PI(e6)

GI(o)

G(o)

GI(i3)

G(i3)

GI(t4)

G(t4)

GI(c3)

G(c3)

GI(c4)

G(c4)

GI(c5)

G(c5)

GI(e5)

G(e5)

GI(c6)

G(c6)

GI(e6)

G(e6)

N(1,4)

TABLE B Linking groups E —CH₂CH₂— V —CH═CH— X —CF═CH— XI —CH═CF— B —CF═CF— T —C≡C— W —CF₂CF₂— Z —CO—O— ZI —O—CO— O —CH₂—O— OI —O—CH₂— Q —CF₂—O— QI —O—CF₂—

TABLE C End groups Left-hand side Right-hand side Used alone -n- C_(n)H_(2n+1)— -n —C_(n)H_(2n+1) -nO- C_(n)H_(2n+1)—O— -nO —O—C_(n)H_(2n+1) -V- CH₂═CH— -V —CH═CH₂ -nV- C_(n)H_(2n+1)—CH═CH— -nV —C_(n)H_(2n)—CH═CH₂ -Vn- CH₂═CH—C_(n)H_(2n+1)— -Vn —CH═CH—C_(n)H_(2n+1) -nVm- C_(n)H_(2n+1)—CH═CH—C_(m)H_(2m)— -nVm —C_(n)H_(2n)—CH═CH—C_(m)H_(2m+1) -N- N≡C— -N —C≡N -S- S═C═N— -S —N═C═S -F- F— -F —F -CL- Cl— -CL —Cl -M- CFH₂— -M —CFH₂ -D- CF₂H— -D —CF₂H -T- CF₃— -T —CF₃ -MO- CFH₂O— -OM —OCFH₂ -DO- CF₂HO— -OD —OCF₂H -TO- CF₃O— -OT —OCF₃ -OXF- CF₂═CH—O— -OXF —O—CH═CF₂ -A- H—C≡C— -A —C≡C—H -nA- C_(n)H_(2n+1)—C≡C— -An —C≡C—C_(n)H_(2n+1) -NA- N≡C—C≡C— -AN —C≡C—C≡N Used in combination with others - . . . A . . . - —C≡C— - . . . A . . . —C≡C— - . . . V . . . - CH═CH— - . . . V . . . —CH═CH— - . . . Z . . . - —CO—O— - . . . Z . . . —CO—O— - . . . ZI . . . - —O—CO— - . . . ZI . . . —O—CO— - . . . K . . . - —CO— - . . . K . . . —CO— - . . . W . . . - —CF═CF— - . . . W . . . —CF═CF— in which n and m each denote integers, and the three dots “ . . . ” are place-holders for other abbreviations from this table.

The following table shows illustrative structures together with their respective abbreviations. These are shown in order to illustrate the meaning of the rules for the abbreviations. They furthermore represent compounds which are preferably used.

TABLE D Illustrative structures The following illustrative structures are compounds, which are particularly preferably employed, having a terminal —NSC group:

The following illustrative structures are compounds, which are preferably additionally used in the media:

The following illustrative structures are auxiliary compounds, which are optionally employed, having three 6-membered rings:

The following illustrative structures are auxiliary compounds, which are optionally employed, having four 6-membered rings:

Illustrative structures of dielectrically neutral compounds which may additionally be employed:

Illustrative structures of further compounds which may additionally be employed:

The following table, Table E, shows illustrative compounds which can be used as stabiliser in the mesogenic media in accordance with the present invention. The total concentration of these and similar compounds in the media is preferably 5% or less.

TABLE E

In a preferred embodiment of the present invention, the mesogenic media comprise one or more compounds selected from the group of the compounds from Table E.

The following table, Table F, shows illustrative compounds which can preferably be used as chiral dopants in the mesogenic media in accordance with the present invention.

TABLE F

C 15

CB 15

CM 21

CM 44

CM 45

CM 47

CC

CN

R/S-811

R/S-1011

R/S-2011

R/S-3011

R/S-4011

R/S-5011

In a preferred embodiment of the present invention, the mesogenic media comprise one or more compounds selected from the group of the compounds from Table F.

The mesogenic media in accordance with the present application preferably comprise two or more, preferably four or more, compounds selected from the group consisting of the compounds from the above tables.

The liquid-crystal media in accordance with the present invention preferably comprise

-   -   seven or more, preferably eight or more, compounds, preferably         compounds having three or more, preferably four or more,         different formulae, selected from the group of the compounds         from Table D.

EXAMPLES

The following examples illustrate the present invention without limiting it in any way.

However, it is clear to the person skilled in the art from the physical properties what properties can be achieved and in what ranges they can be modified. In particular, the combination of the various properties which can preferably be achieved is thus well defined for the person skilled in the art.

Examples 1 to 17 and Comparative Example Comparative Example

A liquid-crystal mixture C-1 having the composition and properties as indicated in the following table is prepared and characterized with respect to its general physical properties and its applicability in microwave

Composition Compound Conc./ No. Abbreviation mass-% 1 PPTUI-3-2 20.0 2 PPTUI-3-4 36.0 3 GGP-3-CL 10.0 4 GGP-5-CL 20.0 5 CPGP-5-2 7.0 6 CPGP-5-3 7.0 Σ 100.0 Physical Properties T(N, I)/° C. = 173 Δn(20° C., 589.3 nm) = 0.335 Δε(20° C., 1 kHz) = 4.6 γ₁ (20° C.)/mPa · s = 746 tan δ_(εr,⊥) (20° C., 19 GHz) = 0.0143 tan δ_(εr,||) (20° C., 19 GHz) = 0.0038 τ (20° C., 19 GHz) = 0.252 η (20° C., 19 GHz) = 17.6

This mixture is suitable for applications in the microwave range, in particular for phase shifters or LC based antenna elements in the micro wave (MW) region, however its response times are only moderate and not sufficient for more demanding applications.

Example 1

A liquid-crystal mixture C-1 having the composition and properties as indicated in the following table is prepared and characterized with respect to its general physical properties and its applicability in microwave components at 19 GHz.

Composition Compound No Abbreviation Conc./mass-% 1 PU-3-S 10.0 2 PTU-3-S 10.0 3 PTU-5-S 10.0 4 CGU-2-S 20.0 5 CGU-4-S 20.0 6 PGU-3-S 16.0 7 PPTU-4-S 7.0 8 PPTU-5-S 7.0 Σ 100.0 Physical Properties T (N, I)/° C. = 123 n_(o) (20° C., 589.3 nm) = t.b.d. Δn (20° C., 589.3 nm) = t.b.d. ε_(∥) (20° C., 1 kHz) = 26.9 Δε (20° C., 1 kHz) = 4.7 γ₁ (20° C.)/mPa · s = 287 k₁ (20° C.)/pN = 14.0 k₃/k₁ (20° C.) = 1.39 V₀ (20° C.)/V = 0.84 ε_(r, ⊥) (20° C., 19 GHz) = 2.36 ε_(r, ∥) (20° C., 19 GHz) = 3.42 tan δ_(ε r, ⊥) (20° C., 19 GHz) = 0.0116 tan δ_(ε r, ∥) (20° C., 19 GHz) = 0.0066 τ (20° C., 19 GHz) = 0.310 η (20° C., 19 GHz) = 26.7 Remarks: t.b.d.: to be determined

This mixture is suitable for applications in the microwave range, in particular for phase shifters or LC based antenna elements in the micro wave (MW) region. In comparison to the comparative examplethis mixture clearly exhibits superior response times.

Examples 1.1 and 1.2

The mixture C-1 is divided into three parts. To each one of two these two parts a certain concentration of the chiral dopant S-1011 as shown in table F above, having a negative value of the HTP, is added.

To one each of these two parts alternatively 0.20% of S-1011 and 0.40% of S-1011 are added, respectively.

The two resultant mixtures are called M-1.1 and M-1.2. These two mixtures each are filled into test cells with antiparallel rubbed glas substrates covered by PI A13046. The test cells have a cell gap of 50 μm.

TABLE 1 Compositions of the mixtures investigated Material C-1 S-1011 Example Mixture Composition Number Concentration/mass-% C-1 100.00 0.00 1.1 99.80 0.20 1.2 99.60 0.40

TABLE 2 Physical Properties (at 20° C.) of the mixtures investigated Mixture C-1 M-1.1 M-1.2 Property Value T (N, I)/° C. t.b.d. t.b.d. t.b.d. Δn (20° C., 589.3 nm) t.b.d. t.b.d. t.b.d. Δε (20° C., 1 kHz) t.b.d. t.b.d. t.b.d. γ₁ (20° C.)/mPa · s t.b.d. t.b.d. t.b.d. V₀/V t.b.d. t.b.d. t.b.d. Remarks: t.b.d.: to be determined, V₀ in 91 μm test cell, described above.

TABLE 3 Microwave characteristics and response times (at 20° C.) of the mixtures investigated Mixture C-1 M-1.1 M-1.2 Property Value tan δ_(ε r, ⊥) (20° C., 19 GHz) t.b.d. t.b.d. t.b.d. tan δ_(ε r, ∥) (20° C., 19 GHz) t.b.d. t.b.d. t.b.d. τ (20° C., 19 GHz) t.b.d. t.b.d. t.b.d. η (20° C., 19 GHz) t.b.d. t.b.d. t.b.d. τ_(on)/s t.b.d. t.b.d. t.b.d. τ_(off)/s 4.1 1.0 0.25 τ_(sum)/s t.b.d. t.b.d. t.b.d. Remarks: t.b.d.: to be determined.

These two mixtures are very highly suitable for applications in the microwave range, in particular for phase shifters or LC based antenna elements in the micro wave (MW) region. Additionally in comparison to the Examples 1.1 and 1.2 these mixtures clearly exhibit superior, i.e. significanly samller, response times. Mixture M-1.2, which is comprisuing the higher concentration of the chiral compound compared to M-1.1, has an even more strongly improved response behaviour.

The switching times are determined from the electro-optical response in test cells with antiparallel rubbed polyimide (PI) orientation layers on top of ITO electrodes on glass substrates. These cells have a cell gap of 91 μm. They are investigated in an optical setup as follows. A test cell is mounted on a temperature-controlled chuck (20° C.) with an antireflective layer between the test cell and the chuck. The test cell is illuminated by a white LED light source from an angle of 45°. No polarizers are used on the test cell.

A rectangular bipolar bias voltage with a frequency of 1 kHz and an amplitude of 100 V is applied to the LC layer in the test cell. This bias voltage is subsequently switched on and off. The test cell is placed in the light path of a microscope (objective lens 5×) and can thus be can be visually observed and inspected. During the switching operation, the brightness of the cell observed through the microscope changes following the changes in the bias voltage. A photodiode installed within the light path of the microscope is used to record the change of the brightness of the LC layer investigated in the test cell via an external photodiode amplifier (Thorlabs PDA200C).

The response times for switching on and for switching off are determined for the time required to change the relative intensity of reflectionfrom 10% to 90% and vice versa, respectively. τ_(on) ≡t(10%)−t(90%) τ_(off) ≡t(90%)−t(10%)

Example 2

A liquid-crystal mixture M-2 having the composition and properties as indicated in the following table is prepared and characterized with respect to its general physical properties and its applicability in microwave components at 19 GHz.

Composition Compound No Abbreviation Conc./mass-% 1 PU-3-S 16.0 2 PVG-4-S 13.0 3 PVG-5-S 13.0 4 PTU-3-S 7.0 5 PTU-5-S 7.0 6 PGU-3-S 24.0 7 PPTU-4-S 10.0 8 PPTU-5-S 10.0 Σ 100.0 Physical Properties T (N, I)/° C. = 100 n_(o) (20° C., 589.3 nm) = t.b.d. Δn (20° C., 589.3 nm) = t.b.d. ε_(∥) (20° C., 1 kHz) = 28.2 Δε (20° C., 1 kHz) = 5.0 γ₁ (20° C.)/mPa · s = 245 tan δ_(ε r, ⊥) (20° C., 19 GHz) = t.b.d. tan δ_(ε r, ∥) (20° C., 19 GHz) = t.b.d. τ (20° C., 19 GHz) = t.b.d. η (20° C., 19 GHz) = t.b.d. Remark: t.b.d.: to be determined. k₁₁=15.8 pN; k₃₃=15.1 V; V₁₀=0.87 V

This mixture is suitable for applications in the microwave range, in particular for phase shifters or LC based antenna elements in the micro wave (MW) region. In comparison to the Comparison Example 1 this mixture clearly exhibits superior response times.

Example 3

A liquid-crystal mixture M-3 having the composition and properties as indicated in the following table is prepared and characterized with respect to its general physical properties and its applicability in microwave components at 19 GHz.

Composition Compound No Abbreviation Conc./mass-% 1 PU-3-S 18.0 2 PVG-4-S 13.0 3 PVG-5-S 13.0 4 PTU-3-S 8.0 5 PTU-5-S 8.0 6 PGU-3-S 20.0 7 PPTU-4-S 10.0 8 PPTU-5-S 10.0 Σ 100.0 Physical Properties T (N, I)/° C. = 93 n_(o) (20° C., 589.3 nm) = t.b.d. Δn (20° C., 589.3 nm) = t.b.d. ε_(∥) (20° C., 1 kHz) = 27.7 Δε (20° C., 1 kHz) = 5.0 γ₁ (20° C.)/mPa · s = 225 tan δ_(ε r, ⊥) (20° C., 19 GHz) = t.b.d. tan δ_(ε r, ∥) (20° C., 19 GHz) = t.b.d. τ (20° C., 19 GHz) = t.b.d. η (20° C., 19 GHz) = t.b.d. Remark: t.b.d.: to be determined. k₁₁=15.0 pN; k₃₃=15.4 V; V₁₀=0.86 V

This mixture is suitable for applications in the microwave range, in particular for phase shifters or LC based antenna elements in the micro wave (MW) region. In comparison to the comparative example this mixture clearly exhibits superior response times.

TABLE 5 Comparison of the properties at 19 GHz and 20° C. Example Liquid crystal Δε_(r⊥) δ_(ε r, ⊥) η 1 M-1 0.56 0.013 14.5 Comparison 5CB 0.026 4.3

Example 4

A liquid-crystal mixture M-4 having the composition and properties as indicated in the following table is prepared.

Composition Compound No Abbreviation Conc./mass-% 1 CP-3-CL 10.0 2 PVG-4-S 11.0 3 PVG-5-S 11.0 4 PTU-3-S 10.0 5 PTU-5-S 10.0 6 CPU-3-S 14.0 7 PGU-3-S 20.0 8 PPTU-4-S 7.0 9 PPTU-5-S 7.0 Σ 100.0 Physical Properties T (N, I)/° C. = 72 n_(e) (20° C., 589.3 nm) = t.b.d. Δn (20° C., 589.3 nm) = t.b.d. ε_(∥) (20° C., 1 kHz) = 24.5 Δε (20° C., 1 kHz) = 5.1 k₁₁ (20° C.)/pN = 11.3 k₃₃ (20° C.)/pN = 13.2 V₀ (20° C.)/V = 0.81 γ₁ (20° C.)/mPa · s = 162 tan δ_(ε r, max) (20° C., 19 GHz) = t.b.d. τ (20° C., 19 GHz) = t.b.d. η (20° C., 19 GHz) = t.b.d. Remark: t.b.d.: to be determined.

This mixture is very highly suitable for applications in the microwave range, in particular for phase shifters or LC based antenna elements in the MW region.

Example 5

A liquid-crystal mixture M-5 having the composition and properties as indicated in the following table is prepared.

Composition Compound No Abbreviation Conc./mass-% 1 PVG-3-S 6.0 2 PVG-4-S 16.0 3 PVG-5-S 6.0 4 PTG-3-S 10.0 5 PTG-5-S 10.0 6 PTU-3-S 8.0 7 PGU-3-S 8.0 8 PPTU-4-S 16.0 9 PPTU-5-S 16.0 Σ 100.0 Physical Properties T (N, I)/° C. = 112 n_(o) (20° C., 589.3 nm) = 1.5454 Δn (20° C., 589.3 nm) = t.b.d. ε_(∥) (20° C., 1 kHz) = 25.7 Δε (20° C., 1 kHz) = 4.4 γ₁ (20° C.)/mPa · s = 270 tan δ_(ε r, ⊥) (20° C., 19 GHz) = 0.0143 tan δ_(ε r, ∥) (20° C., 19 GHz) = 0.0038 τ (20° C., 19 GHz) = 0.252 η (20° C., 19 GHz) = 17.6 Remark: t.b.d.: to be determined.

This mixture is very highly suitable for applications in the microwave range, in particular for phase shifters or LC based antenna elements in the MW region.

Example 6

A liquid-crystal mixture M-6 having the composition and properties as indicated in the following table is prepared.

Composition Compound No Abbreviation Conc./mass-% 1 CP-1V-O1 10.0 2 PVG-4-S 11.0 3 PVG-5-S 11.0 4 PTU-3-S 10.0 5 PTU-5-S 10.0 6 CPU-3-S 14.0 7 PGU-3-S 20.0 8 PPTU-4-S 7.0 9 PPTU-5-S 7.0 Σ 100.0 Physical Properties T (N, I)/° C. = 75.5 n_(e) (20° C., 589.3 nm) = t.b.d. Δn (20° C., 589.3 nm) = t.b.d. ε_(∥) (20° C., 1 kHz) = 24.2 Δε (20° C., 1 kHz) = 5.1 k₁₁ (20° C.)/pN 11.7 k₃₃ (20° C.)/pN 13.6 V₀ (20° C.)/V 0.83 γ₁ (20° C.)/mPa · s = 178 tan δ_(εr, max) (20° C., 19 GHz) = τ (20° C., 19 GHz) = η (20° C., 19 GHz) = Remark: t.b.d.: to be determined.

This mixture is very highly suitable for applications in the microwave range, in particular for phase shifters or LC based antenna elements in the MW region.

Example 7

A liquid-crystal mixture M-7 having the composition and properties as indicated in the following table is prepared.

Composition Compound No Abbreviation Conc./mass-% 1 GGP-3-S 12.0 2 PGG-3-S 8.0 3 PGU-3-S 12.0 4 PVG-3-S 6.0 5 PVG-4-S 16.0 6 PTG-3-S 10.0 7 PTG-5-S 18.0 8 PTU-3-S 10.0 9 PPTU-4-S 6.0 Σ 100.0 Physical Properties T (N, I)/° C. = 98 n_(e) (20° C., 589.3 nm) = t.b.d. Δn (20° C., 589.3 nm) = t.b.d. ε_(∥) (20° C., 1 kHz) = 26.7 Δε (20° C., 1 kHz) = t.b.d. k₁₁ (20° C.)/pN 17.7 k₃₃ (20° C.)/pN 15.7 V₀ (20° C.)/V 0.96 γ₁ (20° C.)/mPa · s = 698 tan δ_(ε r, max) (20° C., 19 GHz) = 0.0189 τ (20° C., 19 GHz) = 0.336 η (20° C., 19 GHz) = 17.9 Remark: t.b.d.: to be determined.

This mixture is very highly suitable for applications in the microwave range, in particular for phase shifters or LC based antenna elements in the MW region.

Examples 8 to 12

To the liquid crystalline medium M-7 of Example 7 alternatively a certain concentration of a further single compound one each is added and the resultant mixtures (M-8 to M-12) are investigated for their general physical properties and for their performance in the microwave regime.

Composition Example Mixture Compound c (Comp.) c (M-4) No. No. Abbreviation /% 7 M-7 None 0.0 100.0 8 M-8 PTPI(c3)TU-4-F 5.0 95.0 9 M-9 PTPI(2)WU-6-F 10.0 90.0 10 M-10 PTPI(2)GU-4-F 10.0 90.0 11 M-11 PTG(c3)TU-4-F 5.0 95.0 12 M-12 PTN(1, 4)TP-3-F 5.0 95.0

Physical Rroperties I, General I (20° C. except T(N.I)) Example Mixture T (N, I)/ No. No. ° C. Δn ε_(∥) Δε 7 M-7 98 t.b.d. 26.7 21.5 8 M-8 98 t.b.d. 26.1 20.9 9 M-9 90 t.b.d. 26.0 21.0 10 M-10 102 t.b.d. 27.0 21.9 11 M-11 93.9 t.b.d. 27.0 21.8 12 M-12 99.5 t.b.d. 25.9 20.9 Remark: t.b.d.: to be determined.

Physical Rroperties II, General II (20° C.) Example Mixture No. No. γ₁ k₁₁/pN k₃₃/pN V₀/V 7 M-7 241 17.7 15.7 0.96 8 M-8 254 15.1 14.6 0.90 9 M-9 272 15.8 15.8 0.91 10 M-10 319 16.0 16.9 0.90 11 M-11 257 15.8 15.0 0.90 12 M-12 273 18.2 15.9 0.99

Physical Rroperties III Microwave I (20° C., 19 GHz) Example Mixture No. No. ε_(r, ⊥) ε_(r, ∥) tan δ_(ε r, ∥) tan δ_(ε r, ⊥) 7 M-7 3.74 2.49 0.0189 0.0091 8 M-8 3.68 2.48 0.0177 0.0088 9 M-9 3.67 2.49 0.0174 0.0084 10 M-10 3.68 2.48 0.0170 0.0082 11 M-11 3.70 2.49 0.0180 0.0088 12 M-12 3.73 2.49 0.0175 0.0085

Physical Rroperties IV, Microwave II (20° C., 19 GHz) Example Mixture No. No. tan δ_(εr,⊥) τ_(εr) η 7 M-7 0.0189 0.336 17.8 8 M-8 0.0177 0.326 18.4 9 M-9 0.0174 0.323 18.6 10 M-10 0.0170 0.327 19.3 11 M-11 0.0180 0.327 18.1 12 M-12 0.0175 0.332 19.0

These mixtures are very well suitable for applications in the microwave range, in particular for phase shifters or LC based antenna elements in the MW region.

The mixtures of examples 7 to 12 are treated and investigated as described under example 1. The resultant mixtures comprising the chiral compound in the respective concentrations show similarly improved properties. They are especially characterized in particular by improved response times.

Example 13

A liquid-crystal mixture M-13 having the composition and properties as indicated in the following table is prepared and characterized with respect to its general physical properties and its applicability in microwave components at 19 GHz.

Composition Compound Conc./ No Abbreviation mass-% 1 PU-3-S 10.0 2 PTU-3-S 10.0 3 PTU-5-S 10.0 4 CGU-2-S 10.0 5 CGU-3-S 10.0 6 CGU-4-S 10.0 7 CGU-5-S 10.0 8 PGU-3-S 16.0 9 PPTU-4-S 7.0 10  PPTU-5-S 7.0 Σ 100.0 Physical Properties T(N, I)/° C. = 126.5 n_(o)(20° C., 589.3 nm) = t.b.d. Δn(20° C., 589.3 nm) = t.b.d. ε_(||)(20° C., 1 kHz) = 27.1 Δε(20° C., 1 kHz) = 4.5 γ₁ (20° C.)/mPa · s = 299 k₁ (20° C.)/pN = 14.8 k₃/k₁ (20° C.) = 1.43 V₀ (20° C.)/V = 0.86 ε_(r,⊥) (20° C., 19 GHz) = 2.36 ε_(r,||) (20° C., 19 GHz) = 3.44 tan δ_(εr,⊥) (20° C., 19 GHz) = 0.0116 tan δ_(εr,||) (20° C., 19 GHz) = 0.0064 τ (20° C., 19 GHz) = 0.315 η (20° C., 19 GHz) = 27.2 Remark: t.b.d.: to be determined.

This mixture is suitable for applications in the microwave range, in particular for phase shifters or LC based antenna elements in the micro wave (MW) region. In comparison to the comparative example this mixture clearly exhibits superior response times.

Example 14

A liquid-crystal mixture M-14 having the composition and properties as indicated in the following table is prepared and characterized with respect to its general physical properties and its applicability in microwave components at 19 GHz.

Composition Compound Conc./ No Abbreviation mass-% 1 PU-3-S 14.0 2 PTU-3-S 14.0 3 CGU-2-S 20.0 4 CGU-4-S 20.0 5 PGU-3-S 18.0 6 PPTU-4-S 7.0 7 PPTU-5-S 7.0 Σ 100.0 Physical Properties T(N, I)/° C. = t.b.d. n_(o)(20° C., 589.3 nm) = t.b.d. Δn(20° C., 589.3 nm) = t.b.d. ε_(||)(20° C., 1 kHz) = t.b.d. Δε(20° C., 1 kHz) = t.b.d. γ₁ (20° C.)/mPa · s = t.b.d. k₁ (20° C.)/pN = t.b.d. k₃/k₁ (20° C.) = t.b.d. V₀ (20° C.)/V = t.b.d. ε_(r,⊥) (20° C., 19 GHz) = t.b.d. ε_(r,||) (20° C., 19 GHz) = t.b.d. tan δ_(εr,⊥) (20° C., 19 GHz) = t.b.d. tan δ_(εr,||) (20° C., 19 GHz) = t.b.d. τ (20° C., 19 GHz) = t.b.d. η (20° C., 19 GHz) = t.b.d. Remark: t.b.d.: to be determined.

This mixture is suitable for applications in the microwave range, in particular for phase shifters or LC based antenna elements in the micro wave (MW) region. In comparison to the comparative example this mixture clearly exhibits superior response times.

Example 15

A liquid-crystal mixture M-15 having the composition and properties as indicated in the following table is prepared and characterized with respect to its general physical properties and its applicability in microwave components at 19 GHz.

Composition Compound Conc./ No Abbreviation mass-% 1 PU-3-S 8.0 2 PVG-4-S 8.0 3 PVG-5-S 8.0 4 PTU-3-S 8.0 5 PTU-5-S 8.0 6 CGU-3-S 10.0 7 CGU-4-S 10.0 8 CGU-5-S 10.0 9 PGU-3-S 16.0 9 PPTU-4-S 7.0 11  PPTU-5-S 7.0 Σ 100.0 Physical Properties T(N, I)/° C. = 121.5 n_(o)(20° C., 589.3 nm) = t.b.d. Δn(20° C., 589.3 nm) = t.b.d. ε_(||)(20° C., 1 kHz) = 26.2 Δε(20° C., 1 kHz) = 4.6 γ₁ (20° C.)/mPa · s = 298 k₁ (20° C.)/pN = 16.0 k₃/k₁ (20° C.) = 1.31 V₀ (20° C.)/V = 0.91 ε_(r,⊥) (20° C., 19 GHz) = 2.36 ε_(r,||) (20° C., 19 GHz) = 3.48 tan δ_(εr,⊥) (20° C., 19 GHz) = 0.0121 tan δ_(εr,||) (20° C., 19 GHz) = 0.0067 τ (20° C., 19 GHz) = 0.321 η (20° C., 19 GHz) = 26.5 Remark: t.b.d.: to be determined.

This mixture is suitable for applications in the microwave range, in particular for phase shifters or LC based antenna elements in the micro wave (MW) region. In comparison to the comparative example this mixture clearly exhibits superior response times.

Example 16

A liquid-crystal mixture M-16 having the composition and properties as indicated in the following table is prepared and characterized with respect to its general physical properties and its applicability in microwave components at 19 GHz.

Composition Compound Conc./ No Abbreviation mass-% 1 PU-3-S 8.0 2 PVG-4-S 8.0 3 PVG-5-S 8.0 4 PTU-3-S 8.0 5 PTU-5-S 8.0 6 CGU-4-S 15.0 7 CGU-5-S 15.0 8 PGU-3-S 16.0 9 PPTU-4-S 7.0 10  PPTU-5-S 7.0 Σ 100.0 Physical Properties T(N, I)/° C. = 124 n_(o)(20° C., 589.3 nm) = t.b.d. Δn(20° C., 589.3 nm) = t.b.d. ε_(||)(20° C., 1 kHz) = 26.2 Δε(20° C., 1 kHz) = 4.6 γ₁ (20° C.)/mPa · s = 311 k₁ (20° C.)/pN = 16.2 k₃/k₁ (20° C.) = 1.28 V₀ (20° C.)/V = 0.91 ε_(r,⊥) (20° C., 19 GHz) = 2.37 ε_(r,||) (20° C., 19 GHz) = 3.48 tan δ_(εr,⊥) (20° C., 19 GHz) = 0.0120 tan δ_(εr,||) (20° C., 19 GHz) = 0.0066 τ (20° C., 19 GHz) = 0.318 η (20° C., 19 GHz) = 26.2 Remark: t.b.d.: to be determined.

This mixture is suitable for applications in the microwave range, in particular for phase shifters or LC based antenna elements in the micro wave (MW) region. In comparison to the comparative example this mixture clearly exhibits superior response times.

Example 17

A liquid-crystal mixture M-17 having the composition and properties as indicated in the following table is prepared and characterized with respect to its general physical properties and its applicability in microwave components at 19 GHz.

Composition Compound Conc./ No Abbreviation mass-% 1 PU-3-S 10.0 2 PTU-3-S 10.0 3 PTU-5-S 10.0 4 CGU-2-S 14.0 5 CGU-3-S 13.0 6 CGU-4-S 13.0 7 PGU-3-S 16.0 8 PPTU-4-S 7.0 9 PPTU-5-S 7.0 Σ 100.0 Physical Properties T(N, I)/° C. = 126.5 n_(o)(20° C., 589.3 nm) = t.b.d. Δn(20° C., 589.3 nm) = t.b.d. ε_(||)(20° C., 1 kHz) = 27.4 Δε(20° C., 1 kHz) = 4.6 γ₁ (20° C.)/mPa · s = 297 k₁ (20° C.)/ = 14.5 k₃/k₁ (20° C.) = 1.45 V₀ (20° C.)/V = 0.84 ε_(r,⊥) (20° C., 19 GHz) = 2.36 ε_(r,||) (20° C., 19 GHz) = 3.44 tan δ_(εr,⊥) (20° C., 19 GHz) = 0.0115 tan δ_(εr,||) (20° C., 19 GHz) = 0.0065 τ (20° C., 19 GHz) = 0.313 η (20° C., 19 GHz) = 27.2 Remark: t.b.d.: to be determined.

This mixture is suitable for applications in the microwave range, in particular for phase shifters or LC based antenna elements in the micro wave (MW) region. In comparison to the comparative example this mixture clearly exhibits superior response times.

Example 18

A liquid-crystal mixture M-18 having the composition and properties as indicated in the following table is prepared and characterized with respect to its general physical properties and its applicability in microwave components at 19 GHz.

Composition Compound Conc./ No Abbreviation mass-% 1 PVG-4-S 16.0 2 PVG-5-S 16.0 3 PTU-3-S 14.0 4 PTU-5-S 10.0 5 PTG-5-S 14.0 6 PGU-3-S 14.0 7 PPTU-4-S 15.0 8 PPTU-5-S 15.0 Σ 100.0 Physical Properties T(N, I)/° C. = 115.5 n_(o)(20° C., 589.3 nm) = t.b.d. Δn(20° C., 589.3 nm) = t.b.d. ε_(||)(20° C., 1 kHz) = 27.0 Δε(20° C., 1 kHz) = 4.5 γ₁ (20° C.)/mPa · s = 304 k₁ (20° C.)/pN/ = t.b.d. k₃/k₁ (20° C.) = t.b.d. V₀ (20° C.)/V = 1.07 ε_(r,⊥) (20° C., 19 GHz) = t.b.d. ε_(r,||) (20° C., 19 GHz) = t.b.d. tan δ_(εr,⊥) (20° C., 19 GHz) = t.b.d. tan δ_(εr,||) (20° C., 19 GHz) = t.b.d. τ (20° C., 19 GHz) = t.b.d. η (20° C., 19 GHz) = t.b.d. Remark: t.b.d.: to be determined.

This mixture is suitable for applications in the microwave range, in particular for phase shifters or LC based antenna elements in the micro wave (MW) region. In comparison to the comparative example this mixture clearly exhibits superior response times.

Example 19

A liquid-crystal mixture M-19 having the composition and properties as indicated in the following table is prepared and characterized with respect to its general physical properties and its applicability in microwave components at 19 GHz.

Composition Compound Conc./ No Abbreviation mass-% 1 PU-3-S 20.0 2 PVG-4-S 16.0 3 PVG-5-S 16.0 4 PGU-3-S 16.0 5 PPTU-4-S 16.0 6 PPTU-5-S 16.0 Σ 100.0 Physical Properties T(N, I)/° C. = 116.5 n_(o)(20° C., 589.3 nm) = t.b.d. Δn(20° C., 589.3 nm) = t.b.d. ε_(||)(20° C., 1 kHz) = 27.7 Δε(20° C., 1 kHz) = 4.6 γ₁ (20° C.)/mPa · s = 292 k₁ (20° C.)/pN = t.b.d. k₃/k₁ (20° C.) = t.b.d. V₀ (20° C.)/V = 1.05 ε_(r,⊥) (20° C., 19 GHz) = t.b.d. ε_(r,||) (20° C., 19 GHz) = t.b.d. tan δ_(εr,⊥) (20° C., 19 GHz) = t.b.d. tan δ_(εr,||) (20° C., 19 GHz) = t.b.d. τ (20° C., 19 GHz) = t.b.d. η (20° C., 19 GHz) = t.b.d. Remark: t.b.d.: to be determined.

This mixture is suitable for applications in the microwave range, in particular for phase shifters or LC based antenna elements in the micro wave (MW) region. In comparison to the comparative example this mixture clearly exhibits superior response times.

Example 20

A liquid-crystal mixture M-20 having the composition and properties as indicated in the following table is prepared and characterized with respect to its general physical properties and its applicability in microwave components at 19 GHz.

Composition Compound Conc./ No Abbreviation mass-% 1 PU-3-S 16.0 2 PVG-4-S 14.0 3 PVG-5-S 14.0 4 PTU-3-S 8.0 5 PTU-5-S 8.0 6 PGU-3-S 14.0 7 PPTU-4-S 10.0 8 PPTU-5-S 10.0 Σ 100.0 Physical Properties T(N, I)/° C. = 95 n_(o)(20° C., 589.3 nm) = t.b.d. Δn(20° C., 589.3 nm) = t.b.d. ε_(||)(20° C., 1 kHz) = 27.4 Δε(20° C., 1 kHz) = 5.0 γ₁ (20° C.)/mPa · s = 234 k₁ (20° C.)/pN = 15.6 k₃/k₁ (20° C.) = 1.00 V₀ (20° C.)/V = 0.88 ε_(r,⊥) (20° C., 19 GHz) = 2.56 ε_(r,||) (20° C., 19 GHz) = 3.68 tan δ_(εr,⊥) (20° C., 19 GHz) = 0.0075 tan δ_(εr,||) (20° C., 19 GHz) = 0.0136 τ (20° C., 19 GHz) = 0.306 η (20° C., 19 GHz) = 22.5 Remark: t.b.d.: to be determined.

This mixture is suitable for applications in the microwave range, in particular for phase shifters or LC based antenna elements in the micro wave (MW) region. In comparison to the comparative example this mixture clearly exhibits superior response times.

Example 21

A liquid-crystal mixture M-21 having the composition and properties as indicated in the following table is prepared and characterized with respect to its general physical properties and its applicability in microwave components at 19 GHz.

Composition Compound Conc./ No Abbreviation mass-% 1 PU-3-S 20.0 2 PVG-4-S 15.0 3 PVG-5-S 15.0 4 PTU-3-S 10.0 5 PGU-3-S 14.0 6 PPTU-4-S 10.0 7 PPTU-5-S 10.0 Σ 100.0 Physical Properties T(N, I)/° C. = 96 n_(o)(20° C., 589.3 nm) = t.b.d. Δn(20° C., 589.3 nm) = t.b.d. ε_(||)(20° C., 1 kHz) = 27.8 Δε(20° C., 1 kHz) = 5.0 γ₁ (20° C.)/mPa · s = 230 k₁ (20° C.)/pN = 15.6 k₃/k₁ (20° C.) = 1.00 V₀ (20° C.)/V = 0.88 ε_(r,⊥) (20° C., 19 GHz) = 2.48 ε_(r,||) (20° C., 19 GHz) = 3.67 tan δ_(εr,⊥) (20° C., 19 GHz) = 0.0083 tan δ_(εr,||) (20° C., 19 GHz) = 0.0152 τ (20° C., 19 GHz) = 0.324 η (20° C., 19 GHz) = 21.0 Remark: t.b.d.: to be determined.

This mixture is suitable for applications in the microwave range, in particular for phase shifters or LC based antenna elements in the micro wave (MW) region. In comparison to the comparative example this mixture clearly exhibits superior response times.

Example 22

A liquid-crystal mixture M-22 having the composition and properties as indicated in the following table is prepared and characterized with respect to its general physical properties and its applicability in microwave components at 19 GHz.

Composition Compound Conc./ No Abbreviation mass-% 1 PU-3-S 10.0 2 PTU-3-S 10.0 3 PTU-5-S 10.0 4 CPU-2-S 20.0 5 CPU-5-S 20.0 6 PGU-3-S 16.0 7 PPTU-4-S 7.0 8 PPTU-5-S 7.0 Σ 100.0 Physical Properties T(N, I)/° C. = 125 n_(o)(20° C., 589.3 nm) = t.b.d. Δn(20° C., 589.3 nm) = t.b.d. ε_(||)(20° C., 1 kHz) = 27.2 Δε(20° C., 1 kHz) = 4.6 γ₁ (20° C.)/mPa · s = 310 k₁ (20° C.)/pN = 14.1 k₃/k₁ (20° C.) = 1.44 V₀ (20° C.)/V = 0.85 ε_(r,⊥) (20° C., 19 GHz) = t.b.d. ε_(r,||) (20° C., 19 GHz) = t.b.d. tan δ_(εr,⊥) (20° C., 19 GHz) = t.b.d. tan δ_(εr,||) (20° C., 19 GHz) = t.b.d. τ (20° C., 19 GHz) = t.b.d. η (20° C., 19 GHz) = t.b.d. Remark: t.b.d.: to be determined.

This mixture is suitable for applications in the microwave range, in particular for phase shifters or LC based antenna elements in the micro wave (MW) region. In comparison to the comparative example this mixture clearly exhibits superior response times.

Example 23

A liquid-crystal mixture M-23 having the composition and properties as indicated in the following table is prepared and characterized with respect to its general physical properties and its applicability in microwave components at 19 GHz.

Composition Compound Conc./ No Abbreviation mass-% 1 PU-3-S 10.0 2 PTU-3-S 10.0 3 PTU-5-S 10.0 4 CPU-2-S 20.0 5 CPU-3-S 20.0 6 PGU-3-S 16.0 7 PPTU-4-S 7.0 8 PPTU-5-S 7.0 Σ 100.0 Physical Properties T(N, I)/° C. = 124 n_(o)(20° C., 589.3 nm) = t.b.d. Δn(20° C., 589.3 nm) = t.b.d. ε_(||)(20° C., 1 kHz) = 27.8 Δε(20° C., 1 kHz) = 4.6 γ₁ (20° C.)/mPa · s = 301 k₁ (20° C.)/pN = 14.1 k₃/k₁ (20° C.) = 1.44 V₀ (20° C.)/V = 0.85 ε_(r,⊥) (20° C., 19 GHz) = t.b.d. ε_(r,||) (20° C., 19 GHz) = t.b.d. tan δ_(εr,⊥) (20° C., 19 GHz) = t.b.d. tan δ_(εr,||) (20° C., 19 GHz) = t.b.d. τ (20° C., 19 GHz) = t.b.d. η (20° C., 19 GHz) = t.b.d. Remark: t.b.d.: to be determined.

This mixture is suitable for applications in the microwave range, in particular for phase shifters or LC based antenna elements in the micro wave (MW) region. In comparison to the comparative example this mixture clearly exhibits superior response times.

Example 24

A liquid-crystal Mixture M-24 having the composition and properties as indicated in the following table is prepared and characterized with respect to its general physical properties and its applicability in microwave components at 19 GHz.

Composition Compound Conc./ No Abbreviation mass-% 1 PU-3-S 10.0 2 PTU-3-S 10.0 3 PTU-5-S 10.0 4 PGU-3-S 16.0 5 PPTU-4-S 7.0 6 PPTU-5-S 7.0 7 CPU-2-S 10.0 8 CPU-3-S 10.0 9 CPU-4-S 10.0 10  CPU-5-S 10.0 Σ 100.0 Physical Properties T(N, I)/° C. = 127 n_(o)(20° C., 589.3 nm) = t.b.d. Δn(20° C., 589.3 nm) = t.b.d. ε_(||)(20° C., 1 kHz) = 27.1 ε_(⊥)(20° C., 1 kHz) = 4.5 γ₁ (20° C.)/mPa · s = 299 k₁ (20° C.)/pN = 14.8 k₃/k₁ (20° C.) = 1.43 V₀ (20° C.)/V = 0.86 ε_(r,⊥) (20° C., 19 GHz) = 2.35 ε_(r,||) (20° C., 19 GHz) = 3.44 tan δ_(εr,⊥) (20° C., 19 GHz) = 0.0116 tan δ_(εr,||) (20° C., 19 GHz) = 0.064 τ (20° C., 19 GHz) = 0.315 η (20° C., 19 GHz) = 27.2 Remark: t.b.d.: to be determined.

This mixture is suitable for applications in the microwave range, in particular for phase shifters or LC based antenna elements in the micro wave (MW) region. In comparison to the comparative example this mixture clearly exhibits superior response times.

Example 25

A liquid-crystal mixture M-25 having the composition and properties as indicated in the following table is prepared and characterized with respect to its general physical properties and its applicability in microwave components at 19 GHz.

Composition Compound Conc./ No Abbreviation mass-% 1 PU-3-S 8.0 2 PVG-4-S 8.0 3 PVG-5-S 8.0 4 PTU-3-S 8.0 5 PTU-5-S 8.0 6 PGU-3-S 16.0 7 PPTU-4-S 7.0 8 PPTU-5-S 7.0 9 CPU-3-S 10.0 10  CPU-4-S 10.0 11  CPU-5-S 10.0 Σ 100.0 Physical Properties T(N, I)/° C. = 122 n_(o)(20° C., 589.3 nm) = t.b.d. Δn(20° C., 589.3 nm) = t.b.d. ε_(||)(20° C., 1 kHz) = 26.2 ε_(⊥)(20° C., 1 kHz) = 4.6 γ₁ (20° C.)/mPa · s = 298 k₁ (20° C.)/pN = 16.0 k₃/k₁ (20° C.) = 1.31 V₀ (20° C.)/V = 0.91 ε_(r,⊥) (20° C., 19 GHz) = 2.36 ε_(r,||) (20° C., 19 GHz) = 3.48 tan δ_(εr,⊥) (20° C., 19 GHz) = 0.0121 tan δ_(εr,||) (20° C., 19 GHz) = 0.0067 τ (20° C., 19 GHz) = 0.321 η (20° C., 19 GHz) = 26.5 Remark: t.b.d.: to be determined.

This mixture is suitable for applications in the microwave range, in particular for phase shifters or LC based antenna elements in the micro wave (MW) region. In comparison to the comparative example this mixture clearly exhibits superior response times.

Example 26

A liquid-crystal mixture M-26 having the composition and properties as indicated in the following table is prepared and characterized with respect to its general physical properties and its applicability in microwave components at 19 GHz.

Composition Compound Conc./ No Abbreviation mass-% 1 PU-3-S 8.0 2 PVG-4-S 8.0 3 PVG-5-S 8.0 4 PTU-3-S 8.0 5 PTU-5-S 8.0 6 PGU-3-S 16.0 7 PPTU-4-S 7.0 8 PPTU-5-S 7.0 9 CPU-4-S 15.0 10  CPU-5-S 15.0 Σ 100.0 Physical Properties T(N, I)/° C. = 124 n_(o)(20° C., 589.3 nm) = t.b.d. Δn(20° C., 589.3 nm) = t.b.d. ε_(||)(20° C., 1 kHz) = 26.2 ε_(⊥)(20° C., 1 kHz) = 4.6 γ₁ (20° C.)/mPa · s = 311 k₁ (20° C.)/pN = 16.2 k₃/k₁ (20° C.) = 1.28 V₀ (20° C.)/V = 0.91 ε_(r,⊥) (20° C., 19 GHz) = 2.37 ε_(r,||) (20° C., 19 GHz) = 3.48 tan δ_(εr,⊥) (20° C., 19 GHz) = 0.0120 tan δ_(εr,||) (20° C., 19 GHz) = 0.0066 τ (20° C., 19 GHz) = 0.318 η (20° C., 19 GHz) = 26.5 Remark: t.b.d.: to be determined.

This mixture is suitable for applications in the microwave range, in particular for phase shifters or LC based antenna elements in the micro wave (MW) region. In comparison to the comparative example this mixture clearly exhibits superior response times.

The mixtures M-2 to M-26 are divided into two parts each. To each one these two mixtures of the respective pairs alternatively 0.20% of S-1011 and 0.40% of S-1011 are added, respectively, as in example 1 an the resultant mixtures are called M-1.1 and M-1.2 are investigated as described under example 1.

The resultant mixtures show similarly improved properties as Examples 1.1 and 1.2, in particular with regard to tunability and figure of merit.

Alternatively to the chiral compound S-1011 also its enantiomer can be used with the same improved effect(s). Also other chiral compounds, e.g. typical chiral dopants for liquid crystal mixtures ma y be beneficially used to achieve essentially the same effect(s). 

The invention claimed is:
 1. Liquid-crystal medium, which comprises one or more chiral compounds in an amount sufficient to improve switching times of the liquid crystal medium and within the range of 0.2% to 0.8% by weight based on the total weight of the liquid-crystal medium and one or more compounds of formula I-2d

in which R¹ denotes alkyl having 1-to 7 carbon atoms, one or more compounds of formulae III-1

and one or more additional compounds of formulae I, II, and III;

in which R¹ denotes H, unfluorinated alkyl or unfluorinated alkoxy having 1 to 17 C atoms or unfluorinated alkenyl, unfluorinated alkenyloxy or unfluorinated alkoxyalkyl having 2 to 15 C atoms, n denotes 1, and

independently of one another, denote

alternatively denotes

in which R² denotes H, unfluorinated alkyl or unfluorinated alkoxy having 1 to 17 C atoms or unfluorinated alkenyl, unfluorinated alkenyloxy or unfluorinated alkoxyalkyl having 2 to 15 C atoms, Z²¹ denotes trans-CH═CH—, trans-CF═CF— or —C≡C—, and

independently of one another, denote

in which R³ denotes H, unfluorinated alkyl or unfluorinated alkoxy having 1 to 17 C atoms or unfluorinated alkenyl, unfluorinated alkenyloxy or unfluorinated alkoxyalkyl having 2 to 15 C atoms, one of Z³¹ and Z³² denotes trans-CH═CH—, trans-CF═CF— or —C≡C— and the other one, independently thereof, denotes trans CH═CH—, trans-CF═CF— or a single bond, and

independently of one another, denote

alternatively independently denotes

and optionally one or more polymerisable compounds of formula P P^(a)-(Sp^(a))_(s1)-(A¹-Z¹)_(n1)-A²-Q-A³-(Z⁴-A⁴)_(n2)-(Sp^(b))_(s2)-P^(b)  P wherein the individual radicals have the following meanings: P^(a) P^(b) each, independently of one another, are a polymerisable group, Sp^(a), Sp^(b) each, independently of one another, denote a spacer group, s1, s2 each, independently of one another, denote 0 or 1, n1, n2 each, independently of one another, denote 0 or 1, Q denotes a single bond, —CF₂O—, —OCF₂—, —CH₂O—, —OCH₂—, —(CO)O—, —O(CO)—, —(CH₂)₄—, —CH₂—CH₂—, —CF₂—CF₂—, —CF₂—CH₂—, —CH₂—CF₂—, —CH═CH—, —CF═CF—, —CF═CH—, —(CH₂)₃O—, —O(CH₂)₃—, —CH═CF—, —C≡C—, —O—, —CH₂—, —(CH₂)₃—, —CF₂—, Z¹, Z⁴ denote a single bond, —CF₂O—, —OCF₂—, —CH₂O—, —OCH₂—, —(CO)O—, —O(CO)—, —(CH₂)₄—, —CH₂—CH₂—, —CF₂—CF₂—, —CF₂—CH₂—, —CH₂—CF₂—, —CH═CH—, —CF═CF—, —CF═CH—, —(CH₂)₃O—, —O(CH₂)₃—, —CH═CF—, —C≡C—, —O—, —CH₂—, —(CH₂)₃—, —CF₂—, where Z¹ and Q or Z⁴ and Q do not simultaneously denote a group selected from CF₂O— and —OCF₂—, A¹, A², A³, A⁴ each, independently of one another, denote a diradical group selected from the following groups: a) the group consisting of trans-1,4-cyclohexylene, 1,4-cyclohexenylene and 1,4′-bicyclohexylene, in which, in addition, one or more non-adjacent CH₂ groups may be replaced by —O— and/or —S— and in which, in addition, one or more H atoms may be replaced by F, b) the group consisting of 1,4-phenylene and 1,3-phenylene, in which, in addition, one or two CH groups may be replaced by N and in which, in addition, one or more H atoms may be replaced by L, c) the group consisting of tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, tetrahydrofuran-2,5-diyl, cyclobutane-1,3-diyl, piperidine-1,4-diyl, thiophene-2,5-diyl and selenophene-2,5-diyl, each of which may also be mono- or polysubstituted by L, d) the group consisting of saturated, partially unsaturated or fully unsaturated, and optionally substituted, polycyclic radicals having 5 to 20 cyclic C atoms, one or more of which may, in addition, be replaced by heteroatoms, selected from the group consisting of bicyclo[1.1.1]pentane-1,3-diyl, bicyclo[2.2.2]octane-1,4-diyl, spiro[3.3]heptane-2,6-diyl,

where, in addition, one or more H atoms in these radicals may be replaced by L, and/or one or more double bonds may be replaced by single bonds, and/or one or more CH groups may be replaced by N, and A³, alternatively may be a single bond, L on each occurrence, identically or differently, denotes F, Cl, CN, SCN, SF₅ or straight-chain or branched, in each case optionally fluorinated, alkyl having 1 to 12 C atoms, if branched is present, then 3 to 12 C atoms, alkoxy having 1 to 12 C atoms, if branched is present, then 3 to 12 C atoms, alkylcarbonyl having 2 to 12 C atoms, if branched is present, then 3 to 12 C atoms, alkoxycarbonyl having 2 to 12 C atoms, if branched is present, then 3 to 12 C atoms, alkylcarbonyloxy having 2 to 12 C atoms, if branched is present, then 3 to 12 C atoms, or-alkoxycarbonyloxy having 2 to 12 C atoms, if branched is present, then 3 to 12 C atoms, R⁰³, R⁰⁴ each, independently of one another, denote H, F or straight-chain or branched alkyl having 1 to 12 C atoms, if branched is present, then 3 to 12 C atoms, in which, in addition, one or more H atoms may be replaced by F, M denotes —O—, —S—, —CH₂—, —CHY¹— or —CY¹Y²—, and Y¹ and Y² each, independently of one another, have one of the meanings indicated above for R⁰³, or denote Cl or CN, and one of the groups Y¹ and Y² alternatively denotes —OCF₃, where the total concentration of the compounds of the formulae I-2d, III-1, I, II and III is from 95% to 99.8% by weight, the concentration of compounds of formula III is from 10% to 40% by weight and the liquid crystal medium has a clearing temperature of 120° C. or more.
 2. Liquid-crystal medium according to claim 1, which comprises one or more chiral compounds having an absolute value of the HTP of 10 μm or more.
 3. Liquid-crystal medium according to claim 2, which comprises one or more chiral compounds selected from the group of compounds of formulae A-I to A-VI:

including the (R,S), (S,R), (R,R) and (S,S) enantiomers, which are not shown,

in which R^(a11) and R^(a12), independently of one another, are alkyl, oxaalkyl or alkenyl having from 2 to 9 carbon atoms, and R^(a11) is alternatively methyl or alkoxy having from 1 to 9 carbon atoms, R^(a21) and R^(a22), independently of one another, are alkyl or alkoxy having from 1 to 9 carbon atoms, oxaalkyl, alkenyl or alkenyloxy having from 2 to 9 carbon atoms, R^(a31) and R^(a32), independently of one another, are alkyl, oxaalkyl or alkenyl having from 2 to 9 carbon atoms, and R^(a11) is alternatively methyl or alkoxy having from 1 to 9 carbon atoms,

are each, independently of one another, 1,4-phenylene, which may also be mono-, di- or trisubstituted by L, or 1,4-cyclohexylene, L is H, F, Cl, CN or optionally halogenated alkyl having 1-7 carbon atoms, alkoxy having 1-7 carbon atoms, alkylcarbonyl having 2-7 carbon atoms, alkoxycarbonyl having 2-7 carbon atoms or alkoxycarbonyloxy having 2-7 carbon atoms, c is 0 or 1, Z⁰ is —COO—, —OCO—, —CH₂CH₂— or a single bond, and R⁰ is alkyl having 1-12 carbon atoms, alkoxy having 1-12 carbon atoms, alkylcarbonyl having 2-12 carbon atoms, alkoxycarbonyl having 2-12 carbon atoms or alkylcarbonyloxy having 2-12 carbon atoms, X¹, X², Y1 and Y² are each, independently of one another, F, Cl, Br, I, CN, SCN, SF₅, straight-chain alkyl having from 1 to 25 carbon atoms or branched alkyl having from 3 to 25 carbon atoms, which may be monosubstituted or polysubstituted by F, Cl, Br, I or CN and in which, in addition, one or more non-adjacent CH₂ groups may each, independently of one another, be replaced by —O—, —S—, —NH—, NR⁰—, —CO—, —COO—, —OCO—, —OCOO—, —S—CO—, —CO—S—, —CH═CH— or —C≡C— in such a way that 0 and/or S atoms are not bonded directly to one another, a polymerisable group or cycloalkyl or aryl having 3 to 20 carbon atoms, which may optionally be monosubstituted or polysubstituted by halogen or by a polymerisable group, x¹ and x² are each, independently of one another, 0, 1 or 2, y¹ and y² are each, independently of one another, 0, 1, 2, 3 or 4, B¹ and B² are each, independently of one another, an aromatic or partially or fully saturated aliphatic six-membered ring in which one or more CH groups may be replaced by N atoms and one or more non-adjacent CH₂ groups may be replaced by O and/or S, W¹ and W² are each, independently of one another, —Z¹-A¹-(Z²-A²)_(m)-R, and one of the two is alternatively R¹ or A³, but both are not simultaneously H, or

U¹ and U² are each, independently of one another, CH₂, O, S, CO or CS, V¹ and V² are each, independently of one another, (CH₂)_(n), in which from one to four non-adjacent CH₂ groups may be replaced by O and/or S, and one of V¹ and V² and, in the case where

both are a single bond, Z¹ and Z² are each, independently of one another, —O—, —S—, —CO—, —COO—, —OCO—, —O—COO—, —CO—NR⁰—, —NR⁰—CO—, —O—CH₂—, —CH₂—O—, —S—CH₂—, —CH₂—S—, —CF₂—O—, —O—CF₂—, —CF₂—S—, —S—CF₂—, —CH₂—CH₂—, —CF₂—CH₂—, —CH₂—CF₂—, —CF₂—CF₂—, —CH═N—, —N═CH—, —N═N—, —CH═CH—, —CF═CH—, —CH═CF—, —CF═C F—, —C≡C—, a combination of two of these groups, where no two O and/or S and/or N atoms are bonded directly to one another, or a single bond, A¹, A² and A³ are each, independently of one another, 1,4-phenylene, in which one or two non-adjacent CH groups may be replaced by N, 1,4-cyclohexylene, in which one or two non-adjacent CH₂ groups may be replaced by O and/or S, 1,3-dioxolane-4,5-diyl, 1,4-cyclohexenylene, 1,4-bicyclo[2.2.2]octylene, piperidine-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl or 1,2,3,4-tetrahydronaphthalene-2,6-diyl, where each of these groups may be monosubstituted or polysubstituted by L, and in addition A¹ is a single bond, L is a halogen atom, CN, NO₂, alkyl having 1-7 carbon atoms, alkoxy having 1-7 carbon atoms, alkylcarbonyl having 2-7 carbon atoms, alkoxycarbonyl having 2-7 carbon atoms or alkoxycarbonyloxy having 2-7 carbon atoms, in which one or more H atoms may be replaced by F or Cl, m is in each case, independently, 0, 1, 2 or 3, and R and R¹ are each, independently of one another, H, F, Cl, Br, I, CN, SCN, SF₅, straight-chain or branched alkyl having from 1 to 25 carbon atoms, if branched is present, then 3 to 25 C atoms, which may optionally be monosubstituted or polysubstituted by F, Cl, Br, I or CN, and in which one or more non-adjacent CH₂ groups may be replaced by —O—, —S—, —NH—, —NR⁰—, —CO—, —COO—, —OCO—, —O—COO—, —S—CO—, —CO—S—, —CH═CH— or —C≡C—, where no two O and/or S atoms are bonded directly to one another, or a polymerisable group.
 4. Liquid-crystal medium according to claim 1, which additionally comprises one or more compounds of the formula I, as indicated in claim
 1. 5. Liquid-crystal medium according to claim 1, which additionally comprises one or more compounds of formula II, as indicated in claim
 1. 6. Liquid-crystal medium according to claim 1, which comprises one or more additional compounds of formulae III, as indicated in claim
 1. 7. Liquid-crystal medium according to claim 1, which in addition to one or more compounds of formula I-2d, one or more compounds of formula III-1 and one or more compounds of formulas I, II and III, comprises one or more additional compounds selected from the group of compounds of formulae I-1, I-2, II-1 to II-3 and III-2 to III-6

in which the parameters have the respective meanings given in claim
 1. 8. Liquid-crystal medium according to claim 1, which comprises a polymerizable compound and optionally additionally comprises a polymerisation initiator.
 9. A method of improving the response time of a liquid-crystal medium comprising using one or more chiral compounds in a liquid-crystal medium in an amount sufficient to improve switching times of the liquid-crystal medium and within the range of 0.2% to 0.8% by weight based on the total weight of the liquid-crystal medium, said liquid crystal medium comprising—one or more compounds of formulae III-1

and one or more additional compounds of formulae I and II and III

in which R denotes H, unfluorinated alkyl or unfluorinated alkoxy having 1 to 17 C atoms or unfluorinated alkenyl, unfluorinated alkenyloxy or unfluorinated alkoxyalkyl having 2 to 15 C atoms, n denotes 1, and

independently of one another, denote

alternatively denotes

in which R² denotes H, unfluorinated alkyl or unfluorinated alkoxy having 1 to 17 C atoms or unfluorinated alkenyl, unfluorinated alkenyloxy or unfluorinated alkoxyalkyl having 2 to 15 C atoms, Z²¹ denotes trans-CH═CH—, trans-CF═CF— or —C≡C—, and

independently of one another, denote

in which R³ denotes H, unfluorinated alkyl or unfluorinated alkoxy having 1 to 17 C atoms or unfluorinated alkenyl, unfluorinated alkenyloxy or unfluorinated alkoxyalkyl having 2 to 15 C atoms, one of Z³¹ and Z³² denotes trans-CH═CH—, trans-CF═CF— or —C≡C— and the other one, independently thereof, denotes trans CH═CH—, trans-CF═CF— or a single bond, and

independently of one another, denote

alternatively independently denotes

and optionally one or more polymerisable compounds of formula P P^(a)-(Sp^(a))_(s1)-(A¹-Z¹)_(n1)-A²-Q-A³-(Z⁴-A⁴)_(n2)-(Sp^(b))_(s2)-P^(b)  P wherein the individual radicals have the following meanings: P^(a), P^(b) each, independently of one another, are a polymerisable group, Sp^(a), Sp^(b) each, independently of one another, denote a spacer group, s1, s2 each, independently of one another, denote 0 or 1, n1, n2 each, independently of one another, denote 0 or 1, Q denotes a single bond, —CF₂O—, —OCF₂—, —CH₂O—, —OCH₂—, —(CO)O—, —O(CO)—, —(CH₂)₄—, —CH₂—CH₂—, —CF₂—CF₂—, —CF₂—CH₂—, —CH₂—CF₂—, —CH═CH—, —CF═CF—, —CF═CH—, —(CH₂)₃O—, —O(CH₂)₃—, —CH═CF—, —C≡C—, —O—, —CH₂—, —(CH₂)₃—, —CF₂—, Z¹, Z⁴ denote a single bond, —CF₂O—, —OCF₂—, —CH₂O—, —OCH₂—, —(CO)O—, —O(CO)—, —(CH₂)₄—, —CH₂—CH₂—, —CF₂—CF₂—, —CF₂—CH₂—, —CH₂—CF₂—, —CH═CH—, —CF═CF—, —CF═CH—, —(CH₂)₃O—, —O(CH₂)₃—, —CH═CF—, —C≡C—, —O—, —CH₂—, —(CH₂)₃—, —CF₂—, where Z¹ and Q or Z⁴ and Q do not simultaneously denote a group selected from CF₂O— and —OCF₂—, A¹, A², A³, A⁴ each, independently of one another, denote a diradical group selected from the following groups: a) the group consisting of trans-1,4-cyclohexylene, 1,4-cyclohexenylene and 1,4′-bicyclohexylene, in which, in addition, one or more non-adjacent CH₂ groups may be replaced by —O— and/or —S— and in which, in addition, one or more H atoms may be replaced by F, b) the group consisting of 1,4-phenylene and 1,3-phenylene, in which, in addition, one or two CH groups may be replaced by N and in which, in addition, one or more H atoms may be replaced by L, c) the group consisting of tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, tetrahydrofuran-2,5-diyl, cyclobutane-1,3-diyl, piperidine-1,4-diyl, thiophene-2,5-diyl and selenophene-2,5-diyl, each of which may also be mono- or polysubstituted by L, d) the group consisting of saturated, partially unsaturated or fully unsaturated, and optionally substituted, polycyclic radicals having 5 to 20 cyclic C atoms, one or more of which may, in addition, be replaced by heteroatoms, selected from the group consisting of bicyclo[1.1.1]pentane-1,3-diyl, bicyclo[2.2.2]octane-1,4-diyl, spiro[3.3]heptane-2,6-diyl,

where, in addition, one or more H atoms in these radicals may be replaced by L, and/or one or more double bonds may be replaced by single bonds, and/or one or more CH groups may be replaced by N, and A³, alternatively may be a single bond, L on each occurrence, identically or differently, denotes F, Cl, CN, SCN, SF₅ or straight-chain or branched, in each case optionally fluorinated, alkyl having 1 to 12 C atoms, if branched is present, then 3 to 12 C atoms, alkoxy having 1 to 12 C atoms, if branched is present, then 3 to 12 C atoms, alkylcarbony having 2 to 12 C atoms, if branched is present, then 3 to 12 C atoms, alkoxycarbonyl having 2 to 12 C atoms, if branched is present, then 3 to 12 C atoms, alkylcarbonyloxy having 2 to 12 C atoms if branched is present, then 3 to 12 C atoms, or alkoxycarbonyloxy having 2 to 12 C atoms, if branched is present, then 3 to 12 C atoms, R⁰³, R⁰⁴ each, independently of one another, denote H, F or straight-chain or branched alkyl having 1 to 12 C atoms, if branched is present, then 3 to 12 C atoms, in which, in addition, one or more H atoms may be replaced by F, M denotes —O—, —S—, —CH₂—, —CHY¹— or —CY¹Y²—, and Y¹ and Y² each, independently of one another, have one of the meanings indicated above for R⁰³, or denote Cl or CN, and one of the groups Y¹ and Y² alternatively denotes —OCF₃ where the total concentration of the compounds of the formulae III-1, I, II and III is from 95% to 99.8%.
 10. Component for high-frequency technology, which comprises a liquid crystal medium according to claim
 1. 11. Component according to claim 10, which is suitable for operation in the microwave range.
 12. Component according to claim 10, which is a phase shifter or a LC based antenna element operable in the microwave region.
 13. A method which comprises including a liquid-crystal medium according to claim 1 in a component for high-frequency technology.
 14. Process for the preparation of a liquid-crystal medium, wherein one or more chiral compounds are mixed with: one or more compounds selected from the group of the compounds of the formulae I, II and III, as specified in claim 1, wherein the amount of one or more chiral compounds is sufficient to improve switching times of the liquid-crystal medium and is within the range of 0.2% to 0.8% by weight based on the total weight of the liquid-crystal medium; and optionally with one or more further compounds and/or with one or more additives.
 15. Microwave antenna array, which comprises one or more components according to claim
 10. 